Phase change inks

ABSTRACT

An ink composition that includes stearyl stearamide, N,N′-ethylene bisoleamide, at least one wax, at least one antioxidant, and at least one solvent dye colorant is useful as a phase change ink.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent applicationSer. No. 12/987,749, filed Jan. 10, 2011, which in turn is a divisionalapplication of U.S. patent application Ser. No. 12/044,514, filed Mar.7, 2008 (now abandoned), the entire disclosures of each applicationbeing incorporated herein by reference.

BACKGROUND

Described herein are amide compounds suitable for use in various inks.The amide compounds described herein may be particularly useful assubstitutes for various known ink vehicles or as supplements to variousknown ink vehicles.

Ink jetting devices are well known in the art. Ink jet printing systemsare generally of two types: continuous stream and drop-on-demand. Incontinuous stream ink jet systems, ink is emitted in a continuous streamunder pressure through at least one orifice or nozzle. The stream isperturbed, causing it to break up into droplets at a fixed distance fromthe orifice. At the break-up point, the droplets are charged inaccordance with digital data signals and passed through an electrostaticfield that adjusts the trajectory of each droplet in order to direct itto a gutter for recirculation or a specific location on a recordingmedium. In drop-on-demand systems, a droplet is expelled from an orificedirectly to a position on a recording medium in accordance with digitaldata signals. A droplet is not formed or expelled unless it is to beplaced on the recording medium. There are generally three types ofdrop-on-demand ink jet systems. One type of drop-on-demand system is apiezoelectric device that has as its major components an ink filledchannel or passageway having a nozzle on one end and a piezoelectrictransducer near the other end to produce pressure pulses. Another typeof drop-on-demand system is known as acoustic ink printing. As is known,an acoustic beam exerts a radiation pressure against objects upon whichit impinges. Thus, when an acoustic beam impinges on a free surface(i.e., liquid/air interface) of a pool of liquid from beneath, theradiation pressure which it exerts against the surface of the pool mayreach a sufficiently high level to release individual droplets of liquidfrom the pool, despite the restraining force of surface tension.Focusing the beam on or near the surface of the pool intensifies theradiation pressure it exerts for a given amount of input power. Stillanother type of drop-on-demand system is known as thermal ink jet, orbubble jet, and produces high velocity droplets. The major components ofthis type of drop-on-demand system are an ink filled channel having anozzle on one end and a heat generating resistor near the nozzle.Printing signals representing digital information originate an electriccurrent pulse in a resistive layer within each ink passageway near theorifice or nozzle, causing the ink vehicle (usually water) in theimmediate vicinity to vaporize almost instantaneously and create abubble. The ink at the orifice is forced out as a propelled droplet asthe bubble expands.

Ink jet printing processes may employ inks that are solid at roomtemperature and liquid at elevated temperatures. Such inks may bereferred to as hot melt inks or phase change inks. In thermal ink jetprinting processes employing hot melt inks, the solid ink is melted bythe heater in the printing apparatus and utilized (for example, jetted)as a liquid in a manner similar to that of conventional thermal ink jetprinting. Upon contact with the printing substrate, the molten inksolidifies rapidly, enabling the colorant to substantially remain on thesurface of the substrate instead of being carried into the substrate(for example, paper) by capillary action, thereby enabling higher printdensity than is generally obtained with liquid inks.

When the amide compounds described herein are utilized in the inkvehicle of a phase change ink, such amide compounds have the ability touse fewer components in the ink vehicle, thereby reducing cost andallowing the ink to be more uniform.

SUMMARY

Disclosed herein is an ink composition comprising an ink vehicle and acolorant, wherein the ink vehicle comprises a compound having a formulaof R¹—CONH—R² or R²—CONH—R¹, wherein R² is an alkyl group having from 1to about 18 carbon atoms and R¹ is an alkyl group having from about 3carbon atoms to about 200 carbon atoms, wherein R² and R¹ have the samenumber of carbon atoms or R² has less carbon atoms than R¹, and whereinat least one of the alkyl groups for R² and R¹ includes at least onehydroxyl group substituent.

Further disclosed is a phase change ink composition comprising an inkvehicle and a colorant, wherein the phase change ink is solid attemperatures of from about 20° C. to about 27° C. and exhibits aviscosity of from about 1 to about 20 centipoise (cP) at an elevatedtemperature at which the phase change ink is to be jetted, wherein theink vehicle comprises a compound having a formula of R¹—CONH—R² orR²—CONH—R¹, wherein R² is an alkyl group having from 1 to about 18carbon atoms and R¹ is an alkyl group having from about 3 carbon atomsto about 200 carbon atoms, wherein R² and R¹ have the same number ofcarbon atoms or R² has less carbon atoms than R¹, and wherein at leastone of the alkyl groups for R² and R¹ includes at least one hydroxylgroup substituent.

EMBODIMENTS

The phase change inks herein include an ink vehicle that is solid attemperatures of from about 20° C. to about 27° C., for example roomtemperature, and specifically are solid at temperatures below about 40°C. However, the inks change phase upon heating, and are in a moltenstate at jetting temperatures. Thus, the inks have a viscosity of fromabout 1 to about 20 centipoise (cP), such as from about 5 to about 15 cPor from about 8 to about 12 cP, at an elevated temperature suitable forink jet printing, such as temperatures of from about 50° C. to about150° C., such as from about 70° C. to about 130° C. or from about 80° C.to about 120° C.

In one embodiment, the ink compositions have melting points of no lowerthan about 40° C., in another embodiment of no lower than about 60° C.,and in yet another embodiment of no lower than about 80° C., and havemelting points in one embodiment of no higher than about 160° C., inanother embodiment of no higher than about 140° C., and in yet anotherembodiment of no higher than about 100° C., although the melting pointcan be outside of these ranges. The ink compositions disclosed hereingenerally have melt viscosities at the jetting temperature, in oneembodiment no lower than about 75° C., in another embodiment no lowerthan about 100° C., and in yet another embodiment no lower than about120° C., and in one embodiment no higher than about 180° C., and inanother embodiment no higher than about 150° C., although the jettingtemperature can be outside of these ranges, in one embodiment of no morethan about 30 centipoise, in another embodiment of no more than about 20centipoise, and in yet another embodiment of no more than about 15centipoise, and in one embodiment of no less than about 2 centipoise, inanother embodiment of no less than about 5 centipoise, and in yetanother embodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

Disclosed herein are amide compounds suitable for use in phase change,low energy ink vehicles.

Alkyl Amides

In a first embodiment, the ink vehicle compound is a compound having aformula of R¹—CONH—R² or a formula of R²—CONH—R¹, wherein R² is alkylgroup having from 1 to about 18 carbon atoms and R¹ is a straight chainor branched alkyl group having from about 3 carbon atoms to about 200carbon atoms, and wherein R² and R¹ have the same number of carbon atomsor R² has less carbon atoms than R¹.

R² may be an alkyl group having from 1 to about 18 carbon atoms, such asfrom 1 to about 15 carbon atoms or from 1 to about 10 carbon atoms. R²may be a linear, branched, saturated, unsaturated, substituted, orunsubstituted alkyl group, and wherein heteroatoms such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present as substitutions in the alkyl group. Further, R² mayinclude any suitable substituents, such as hydroxy groups, halogenatoms, amine groups, imine groups, ammonium groups, azo groups, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, carboxylic acid groups, ester groups, amidegroups, carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonategroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, cyanato groups, isocyanato groups, thiocyanato groups,isothiocyanato groups, mixtures thereof, and the like. For example, R²may be an alkyl group selected from methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl,t-pentyl, neopentyl, hexyl (including all isomers), heptyl (includingall isomers), octyl (including all isomers), nonyl (including allisomers), decyl (including all isomers), undecyl (including allisomers), dodecyl (including all isomers), tridecyl (including allisomers), tetradecyl (including all isomers), pentadecyl (including allisomers), hexadecyl (including all isomers), heptadecyl (including allisomers) and octadecyl (including all isomers).

In embodiments, R¹ is a straight chain or branched chain alkyl grouphaving from about 3 carbon atoms to about 200 carbon atoms, such as fromabout 5 carbon atoms to about 150 carbon atoms or from about 15 carbonatoms to about 100 carbon atoms. In embodiments, the straight chain orbranched alkyl group of R¹ may have hydroxyl substitutions and optionalheteroatoms, where suitable. However, in an embodiment, if R¹ is astraight chain alkyl group having no hydroxyl substituents, it is thendesirable that no other substitutions and no heteroatoms be present.

Specifically, in embodiments, R² is CH₃ and the compound will have aformula of

The alkyl amide compound having a formula of R¹—CONH—R² or R²—CONH—R¹may be derived by reacting a sufficient amount of an alkyl amine with asufficient amount of a straight chain carboxylic acid or a branchedcarboxylic acid to ensure that the alkyl amide compound of the presentembodiment is obtained. This reaction occurs at a temperature in a rangeof from about 80° C. to about 220° C., such as from about 85° C. toabout 215° C. or from about 90° C. to about 180° C. The straight chainor branched carboxylic acid may optionally include hydroxyl substituentsor heteroatoms depending upon the desired alkyl amide. In embodiments,the compound having a formula of R¹—CONH—R² may be obtained by, forexample, reacting R¹—CO₂H and H₂N—R².

The alkyl amide compound having a formula of R¹—CONH—R² or R²—CONH—R¹may be utilized as an ink vehicle in a solid phase change ink becauseits melting characteristics are suitable for use in phase change inks.The compound when R¹ has no hydroxyl group substituents exhibits both acrystalline and an amorphous portion. Specifically, the portion of thecompound derived from the straight-chain carboxylic acid, that isderived from R¹, is crystalline, which decreases viscosity; however, theportion of the compound derived from the alkyl amine, that is derivedfrom R², is amorphous, which improves hardness. Thus, the alkyl amidecompound having a formula of R¹—CONH—R² or R²—CONH—R¹, when R¹ has nohydroxyl group substituents, can exhibit both improved viscosity andhardness compared to phase change inks not having the alkyl amidecompound of formula R¹—CONH—R² or R²—CONH—R¹ described herein.

When the alkyl amide compound disclosed herein is derived fromstraight-chain carboxylic acids, the alkyl amide compound may be ahighly crystalline material with viscosities of from about 0.01 cps toabout 25 cps, such as from about 0.1 cps to about 15 cps or from about 1cps to about 10 cps at about 140° C. The heat of fusion of an alkylamide compound derived from a straight chain carboxylic acid may be ofgreater than about 100 J/g, such as greater than 125 J/g or greater than150 J/g, as measured by a Differential Scanning calorimeter Q1000 madeby TA Instruments at a constant heating and cooling rate of about 10°C./min. The hardness of such alkyl amide compounds as measured with aKoehler K95500 Digital Penetrometer according to ASTM D1321 is fromabout 0.01 dmm (decimillimeters) to about 75 dmm, such, as from about0.1 dmm to about 50 dmm or from about 0.5 dmm to about 25 dmm.

Alkyl amide compounds having a hydroxyl functionality, that is derivedfrom, for example, hydroxystearic acid or aleuritic acid, are solid withviscosities of from about 100 cps to about 5000 cps, such as from about100 cps to about 1000 cps or from about 100 cps to about 500 cps at atemperature of about 140° C.

Alkyl amide compounds derived from branched acids may be liquid or solidat room temperature. For example, an alkyl amide compound derived from,for example, isostearic acid or 2-ethylhexanoic acids, may be liquid atroom temperature, that is, approximately 25° C., with a viscosity offrom about 0.01 cps to about 25 cps, such as from about 0.1 cps to about15 cps or from about 1 cps to about 10 cps. In alternative examples, analkyl amide compound derived from, for example, Isocarb 24 acid, may besolid at room temperature, that is, approximately 25° C., withviscosities of from about 100 cps to about 5000 cps, such as from about100 cps to about 1000 cps or from about 100 cps to about 500 cps.

The alkyl amides described herein may be utilized in known inkformulations in addition to the known ink vehicles or as a replacementfor a portion of the ink vehicle. For example, alkyl amides derived fromstraight chained or branched carboxylic acid having at least onehydroxyl substituent could replace or supplement rosin esters in knownink formulations while straight chained alkyl amides derived fromstraight chained or branched carboxylic acid not having any hydroxylsubstituents could replace or supplement the waxes used in known inkformulations.

In embodiments, it is desired that the amide (NH) group of the compoundbe close to the end group of the compound because such a location of theamide (NH) group improves the polarity of the compound. Thus, where R¹includes greater than about 5 carbon atoms, the configuration “close to”in this regard refers to, for example, the amide (NH) group being withinabout 5 carbons or less of the end of the compound. R¹—CONH—R² may bemore desired in terms of polarity to the configuration R²—CONH—R¹. Thus,when the compound is utilized in an ink vehicle, polar colorants arebetter solubulized when the ink vehicle has polar groups, such as theamine group of the disclosed compound.

Examples of alkyl amides having a formula of R¹—CONH—R² or R²—CONH—R¹disclosed herein include:

wherein n is, for example, from 0 to about 195, including 0 (R¹ derivedfrom stearic acid), 2 (R¹ derived from UNICID 350 or behenic acid), 5(R¹ derived from UNICID 425), 10 (R¹ derived from UNICID 550) or 15 (R¹derived from UNICID 700);

wherein n is, for example, from 0 to 195, and including 0 (R¹2-ethylhexanoic acid), 1 (R¹ derived from 12 carbon Guerbet acid), 2 (R¹derived from 16 carbon Guerbet acid), 3 (R¹ derived from 20 carbonGuerbet acid), 4 (R¹ derived from 24 carbon Guerbet acid) or 7 (R¹derived from 36 carbon Guerbet acid).

Di-Amides

In further embodiments, disclosed herein is a di-amide compound having aformula of R¹—CONH—R⁶—CONH—R³, R¹—NHCO—R⁶—CONH—R³, R¹—CONH—R⁶—NHCO—R³ orR¹—NHCO—R⁶—NHCO—R³, wherein the compound is suitable for use in phasechange ink compositions, and wherein R⁶ is cyclic group having fromabout 5 to about 8 carbon atoms and R¹ and R³ are the same or differentand comprise straight chain or branched alkyl group having from about 3carbon atoms to about 200 carbon atoms.

In embodiments, R¹ and R³ may be the same or different and comprise astraight chain or branched alkyl group having from about 3 carbon atomsto about 200 carbon atoms, such as from about 5 carbon atoms to about150 carbon atoms or from about 15 carbon atoms to about 100 carbonatoms. In embodiments, the alkyl group of R¹ or R³ may have hydroxylsubstitutions and optional heteroatoms, where suitable. For example, ifR¹ or R³ is a straight chain alkyl, then that alkyl will have nosubstitutions and no heteroatoms. However if R¹ or R³ is a branchedalkyl having a hydroxyl substituent, then that R¹ or R³ may havesubstitutions such as heteroatoms, in addition to any hydroxylsubstituents. Although R¹ and R³ may be the same type of alkyl, inspecific embodiments R¹ and R³ are not the same type of alkyl, forexample, one of R¹ and R³ may be a branched alkyl while the other of R¹or R³ may be a straight chain alkyl, or one of R¹ and R³ may be an alkylhaving a hydroxyl substituent while the other of R¹ or R³ may be astraight chain alkyl, or one of R¹ and R³ may be a branched alkyl whilethe other of R¹ or R³ may be an alkyl having a hydroxyl substituent.

R⁶ may be a structure of diaminocyclohexane having a formula of:

For example, the cyclic di-amides disclosed herein may have a structureof

However, R⁶ is not limited to cyclohexanes, but may also be acyclopentane, cycloheptane or cyclooctane, and the amines can be presentin 1,2 positions, 1,3 positions or 1,4 positions, and may be in the cisposition or trans position. R⁶ can also be an aromatic, an aryl alkyl,an alkyl aryl, and may be substituted or include heteroatoms, asdescribed herein.

The compound having a formula of R¹—CONH—R⁶—CONH—R³, R¹—NHCO—R⁶—CONH—R³,R¹—CONH—R⁶—NHCO—R³ or R¹—NHCO—R⁶—NHCO—R³, may be derived by reacting asufficient amount of an alkyl amine with a sufficient amount of astraight chain dicarboxylic acid to ensure that the di-amide compound ofthis embodiment is obtained. This reaction occurs at a temperature in arange of from about 80° C. to about 220° C., such as from about 85° C.to about 215° C. or from about 90° C. to about 210° C. In embodiments,the compound having a formula of R¹—NHCO—R⁶—CONH—R³ may be derived byreacting R¹—CO₂H, R³—CO₂H and H₂N—R⁶—H₂N.

The di-amide compound having a formula of R¹—CONH—R⁶—CONH—R³,R¹—NHCO—R⁶—CONH—R³, R¹—CONH—R⁶—NHCO—R³ or R¹—NHCO—R⁶—NHCO—R³, may beutilized as an ink vehicle, or may replace or supplement known inkcomponents, such as rosin esters, triamides and tetra-amides. When atleast one of R¹ or R³ is a branched alkyl, then such a compound exhibitsimproved adhesiveness and flexibility, for example because the branchingleads to a higher amorphous content. Such di-amide compounds having atleast one of R¹ or R³ being a branched alkyl exhibit a low heat offusion, for example, from about 5 J/g to about 60 J/g, or from about 8J/g to about 55 J/g or from about 10 J/g to about 50 J/g.

Di-amides compounds derived from straight chain acids are hard at roomtemperature with a hardness as measured with a Koehler K95500 DigitalPenetrometer according to ASTM D1321 being from about 0.01 dmm to about5 dmm, such as from about 0.1 dmm to about 3.5 dmm or from about 0.5 dmmto about 2 dmm. The viscosities of such di-amide compounds at about 140°C. may be from about 5 cps to about 50 cps, such as from about 8 cps toabout 40 cps or from about 10 to about 30 cps. Due to their molecularconformation and their ability to form hydrogen bonds, these materialshave relatively high melting and crystallization temperatures of greaterthan 90° C., such as greater than 100° C. or greater than 110° C.

Di-amide compounds derived from branched carboxylic acids, such asisostearic acid, have viscosities of from about 1 cps to about 500 cps,such as from about 5 cps to about 250 cps or from about 10 cps to about100 cps at about 140° C. The non-linear molecular conformation of boththe trans-1,2-diaminocyclohexane as well as the branched carboxylic acidleads to the formation of materials with low degrees of crystallinityand low heat of fusion of, for example, from about 5 J/g to about 60J/g, or from about 8 J/g to about 55 J/g or from about 10 J/g to about50 J/g. While the crystalline portion of such a di-amide compounds maycontribute to a low viscosity, the amorphous chains may inhibit thegrowth of the crystalline domains. As a consequence, these types ofmaterials may display a high degree of flexibility and transparency.They are also thermally stable and display an excellent adhesion tosubstrates due to the high degree of hydrogen bonding and theirpermanent flexibility.

Di-amide compounds derived from hydroxyl containing acids may betransparent solids at room temperature, about 25° C. They have lowermelting and crystallization transitions than those di-amide compoundsderived from straight chain acids with a heat of fusion of from about 5J/g to about 60 J/g, or from about 8 J/g to about 55 J/g or from about10 J/g to about 50 J/g.

It is further desired that the amine group of the compound be close tothe end group of the compound because such a location of the amine groupimproves the polarity of the compound. In other words, the term “close”refers to the amine group of the compound being within about 5 carbonsor less of the end of the compound. Thus, when the compound is utilizedin an ink vehicle, polar colorants are better solubilized when the inkvehicle has polar groups, such as the amine group of the disclosedcompound.

Examples of di-amides having a formula of R¹—CONH—R⁶NHCO—R disclosedherein include:

wherein n is, for example, from 0 to about 195, including 0 (R¹ derivedfrom stearic acid), 2 (R¹ derived from UNICID 350 or behenic acid), 5(R¹ derived from UNICID 425), 10 (R¹ derived from UNICID 550) or 15 (R¹derived from UNICID 700); and

Tetra-Amide

In further embodiments, disclosed herein is a tetra-amide compoundhaving a formula of R¹—CONH—R⁶—CONH—C₃₄H₆₄÷_(n)—CONH—R⁶—CONH—R³,R¹—NHCO—R⁶—NHCO—C₃₄H_(64+n)—NHCO—R⁶—NHCO—R³,R¹—CONH—R⁶—NHCO—C₃₄H_(64+n)—CONH—R⁶—NHCO—R³ orR¹—NHCO—R⁶—CONH—C₃₄H_(64+n)—NHCO—R⁶—CONH—R³, wherein R⁶ is the same ordifferent cyclic group having from about 5 to about 8 carbon atoms andR¹ and R³ are the same or different and comprise straight chain orbranched alkyl group having from about 3 carbon atoms to about 200carbon atoms.

R⁶ may have a structure as defined above for the di-amide disclosedherein. R⁶ may also be a cyclopentane, cyclohexane, cycloheptane orcyclooctane, and the amine groups may be present at the 1,2 positions,1,3 positions, 1,4 positions, or 1,5 positions (depending upon thecyclic structure) and may be in the cis position or trans position. R⁶can also be an aromatic, an aryl alkyl, an alkyl aryl, and may besubstituted or include heteroatoms, as described herein. For example, R⁶may be 1,2-trans-diaminocyclohexane having a formula of:

In embodiments, R¹ and R³ may be the same or different and comprise astraight chain or branch chained alkyl group having from about 3 carbonatoms to about 200 carbon atoms, such as from about 5 carbon atoms toabout 150 carbon atoms or from about 15 carbon atoms to about 10 carbonatoms. In embodiments, the alkyl group of R¹ or R³ may have hydroxylsubstituents and substitutions such as optional heteroatoms, wheresuitable. For example, if R¹ or R³ is a straight chain alkyl, then thatalkyl will have no substituents or substitutions, such as heteroatoms.However, if or R¹ or R³ is a branched alkyl having a hydroxylsubstituent, then that R¹ or R³ may have substituents, in addition toany hydroxyl substituents, and optionally may include substitutions,such as heteroatoms. R¹ and R³ do not have to be the same type of alkyl,for example, one of R¹ and R³ may be a branched alkyl while the other ofR¹ or R³ may be a straight chain alkyl, or one of R¹ and R³ may be analkyl having a hydroxyl substituent while the other of R¹ or R³ may be astraight chain alkyl, or one of R¹ and R³ may be a branched alkyl whilethe other of R¹ or R³ may be an alkyl having a hydroxyl substituent.

A dimer acid suitable for use herein may have a formula ofCO₂H—C₃₄H_(64+n)—CO₂H, the dimer acid may be a branched alkylene groupwhich may include unsaturations and cyclic groups, wherein n is aninteger of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

The tetra-amides disclosed herein may have a formula of:

For example, the tetra-amide compound described herein may have thegeneral formula of

The tetra-amide compound having the above formula may be derived byreacting sufficient amounts of a dimer acid, a cyclic di-amine andcarboxylic acid to ensure that the tetra-amide compound of thisembodiment is derived. This reaction occurs at a temperature in a rangeof from about 80° C. to about 220° C., such as from about 85° C. toabout 215° C. or from about 90° C. to about 210° C. In embodiments, thetetra-amide compound may be derived by reacting,

R¹—CO₂H, and

R³—CO₂H, wherein R¹ and R³ are defined as above.

The tetra-amide compound having a formula ofR¹—CONH—R⁶—CONH—C₃₄H_(64+n)—CONH—R⁶—CONH—R³,R¹—CONH—R⁶—NHCO—C₃₄H_(64+n)—CONH—R⁶—NHCO—R³,R¹—NHCO—R⁶—CONH—C₃₄H_(64+n)—NHCO—R⁶—CONH—R³,R¹—NHCO—R⁶—NHCO—C₃₄H_(64+n)—CONH—R⁶—CONH—R³, andR¹—CONH—R⁶—CONH—C₃₄H_(64+n)—NHCO—R⁶—NHCO—R³, may be utilized as a phasechange ink vehicle. When at least one of R¹ or R³ is a branched alkyl,such a compound exhibits unexpected results over existing triamidecomponents and existing tetra-amide components used in known inkformulations, such as improved adhesiveness and flexibility, for examplebecause the branching leads to a higher amorphous content. Thetetra-amide described herein may be utilized in known ink formulationsas a replacement for or a supplement to known rosin esters, knowntriamides and known tetra-amides.

Tetra-amide compounds derived from straight chain acids are very hard atroom temperature, about 25° C., with a hardness measured with a KoehlerK95500 Digital Penetrometer according to ASTM D1321 being from about0.01 dmm (decimillimeters) to about 5 dmm, such as from about 0.1 dmm toabout 3 dmm or from about 0.5 dmm to about 1 dmm. Their viscosities atabout 140° C. may be from about 25 cps to about 600 cps, such as fromabout 40 cps to about 400 cps or from about 50 cps to about 200 cps,depending upon the chain length of the acid used. The longer straightchain acids lead to materials with higher degrees of crystallinity,lower melt viscosities and are more opaque, with heat of fusion that canrange from about 25 J/g to about 600 J/g, or from about 50 J/g to about400 J/g or from about 100 J/g to about 200 J/g. The tetra-amidecompounds with shorter straight chain acids are more amorphous, havehigher viscosities and at the same time exhibit improved transparencyand heat of fusion that can range from about 5 J/g to about 60 J/g, orfrom about 8 J/g to about 55 μg or from about 10 J/g to about 50 J/g.

In tetra-amide compounds derived from branched carboxylic acid, the useof 1,2-trans-diaminocyclohexane in the synthesis of tetra-amides leadsto materials that have a higher amorphous component and as a result,they are hard and transparent. The use of branched carboxylic acidscontributes even more to a disruption of the chain linearity and leadsto materials that range from semicrystalline to amorphous. Suchtetra-amide compounds derived from branched carboxylic acids have alower melting point transitions as well as improved toughness. They mayhave viscosities of from about 25 cps to about 1000 cps, such as fromabout 50 cps to about 750 cps or from about 100 cps to about 500 cps ata temperature of about 140° C. The non-linear molecular conformation ofboth the trans-1,2-diaminocyclohexane as well as the branched carboxylicacid leads to the formation of materials with low degrees of,crystallinity and low heat of fusion that can range from about 5 J/g toabout 60 J/g, or from about 8 J/g to about 55 J/g or from about 10 J/gto about 50 J/g.

Tetra-amide compounds derived from hydroxyl containing carboxylic acidshave similar properties to tetra-amide compounds derived from branchedcarboxylic acids except that viscosities can range from about 25 cps toabout 5000 cps, such as from about 50 cps to about 2500 cps or fromabout 100 cps to about 1000 cps at a temperature of 140° C., and a heatof fusion that can range from about 5 J/g to about 60 J/g, or from about8 J/g to about 55 J/g or from about 10 J/g to about 50 J/g.

Examples of tetra-amide compounds having a formula ofR¹—CONH—R⁶—CONH—C₃₄H_(64+n)—CONH—R⁶—CONH—R³,R¹—CONH—R⁶—NHCO—C₃₄H_(64+n)—CONH—R⁶—NHCO—R³ orR¹—NHCO—R⁶—CONH—C₃₄H_(64+n)—NHCO—R⁶—CONH—R³,R¹—NHCO—R⁶—NHCO—C₃₄H_(64+n)—CONH—R⁶—CONH—R³, andR¹—CONH—R⁶—CONH—C₃₄H_(64+n)—NHCO—R⁶—NHCO—R³, disclosed herein include:

wherein n is, for example, from 0 to about 195, including 0 (R¹ derivedfrom stearic acid), 2 (R¹ derived from UNICID 350 or behenic acid), 5(R¹ derived from UNICID 425), 10 (R¹ derived from UNICID 550) or 15 (R¹derived from UNICID 700);

wherein n is, for example, from 0 to about 195, and including 0 (derivedfrom 2-ethyl hexanoic acid), 1 (derived from 12 carbon Guerbet acid), 2(derived from 16 carbon Guerbet acid), 3 (20 carbon Guerbet acid), 4(derived from 24 carbon Guerbet acid) or 7 (derived from 36 carbonGuerbet acid).

In yet further embodiments, disclosed is a tetra-amide compound having aformula of R¹—CONH—R⁴—CONH—C₃₄H_(64+n)—CONH—R⁵—CONH—R³,R¹—CONH—R⁴—NHCO—C₃₄H_(64+n)—CONH—R⁵—NHCO—R³ orR¹—NHCO—R⁴—CONH—C₃₄H_(64+n)—NHCO—R⁵—CONH—R³,R¹—NHCO—R⁴—NHCO—C₃₄H_(64+n)—CONH—R⁵—CONH—R³, orR¹—CONH—R⁴—CONH—C₃₄H_(64+n)—NHCO—R⁵—NHCO—R³, wherein R¹ and R³ are thesame as described above for other tetra-amide compounds. R¹ and R³ mayboth be derived from isostearic acid.

R⁶ in the tetra-amides described above are replaced with R⁴ or R⁵, whichmay be the same or different alkylene having from 1 to about 200 carbonatoms, such as from about 3 to about 150 carbon atoms or from about 5 toabout 100 carbon atoms.

For example, a tetra-amide compound having a formula ofR¹—CONH—R⁴—CONH—C₃₄H_(64+n)—CONH—R⁵—CONH—R³,R¹—CONH—R⁴—NHCO—C₃₄H_(64+n)—CONH—R⁵—NHCO—R³ orR¹—NHCO—R⁴—CONH—C₃₄H_(64+n)—NHCO—R⁵—CONH—R³,R¹—NHCO—R⁴—NHCO—C₃₄H_(64+n)—CONH—R⁵—CONH—R³, orR¹—CONH—R⁴—CONH—C₃₄H_(64+n)—NHCO—R⁵—NHCO—R³ may be

Each of the amide compounds described herein may be present in a phasechange ink as an ink vehicle in any suitable amount. Specifically, anyof the amide compounds may be present alone or in combination in anamount of from about 5 weight percent to about 100 weight percent of theink vehicle of the phase change ink, such as from about 10 weightpercent to about 95 weight percent of the ink vehicle of the phasechange ink or from about 15 weight percent to about 90 weight percent ofthe ink vehicle of the phase change ink.

Additional Ink Components

Any additional suitable ink vehicle components may be employed, althoughas above it may be desirable for the amide compound to comprisesubstantially all of the ink vehicle. Additional suitable ink vehiclematerials can include paraffins, microcrystalline waxes, polyethylenewaxes, ester waxes, fatty acids and other waxy materials, fatty amidecontaining materials, sulfonamide materials, resinous materials madefrom different natural sources (tall oil rosins and rosin esters, forexample), and many synthetic resins, oligomers, polymers, and copolymerssuch as further discussed below, and mixtures thereof.

Examples of suitable additional specific ink vehicle materials include,for example, ethylene/propylene copolymers, such as those available fromPetrolite and of the general formula

wherein z represents an integer from 0 to about 30, such as from 0 toabout 20 or from 0 to about 10, y represents an integer from 0 to about21, such as from 0 to about 20 or from 0 to about 10 and x is equal toabout 21-y. The distribution of the side branches may be random alongthe carbon chain. The copolymers may have, for example, a melting pointof from about 70° C. to about 150° C., such as from about 80° C. toabout 130° C. or from about 90° C. to about 120° C. and a molecularweight range of from about 500 to about 4,000. Commercial examples ofsuch copolymers include, for example, Petrolite CP-7 (Mn=650), PetroliteCP-11 (Mn=1,100, Petrolite CP-12 (Mn=1,200) and the like. When present,the ethylene/propylene copolymers may be present in an amount of fromabout 1 percent to about 80 percent by weight of the ink vehicle, inanother embodiment from about 3 percent to about 70 by weight of the inkvehicle, in yet another embodiment at least about 5 percent to about 60percent by weight of the ink vehicle.

Urethane, urea, amide and imide derivatives of oxidized synthetic orpetroleum waxes, such as those available from Petrolite and of thegeneral formulas

wherein R is an alkyl group of the formula CH₃(CH₂)_(n), n is an integerof from about 5 to about 400, for example from about 10 to about 300 orfrom about 20 to about 200 and R¹ is a tolyl group, may also be used asthe ink vehicle. In embodiments, the urethane, urea, amide and imidederivatives may be linear, branched, cyclic and any combination thereof.These materials may have a melting point of from about 60° C. to about120° C., such as from about 70° C. to about 100° C. or from about 70° C.to about 90° C. Commercial examples of such materials include, forexample, PETROLITE CA-11 (Mn=790, Mw/Mn=2.2), PETROLITE WB-5 (Mn=650,Mw/Mn=1.7), PETROLITE WB-17 (Mn=730, Mw/Mn=1.8), and the like.

When present, urethane resin may be present in the ink in one embodimentin an amount of from about 1 percent to about 80 percent by weight ofthe ink vehicle, in another embodiment from about 3 percent to about 70by weight of the ink vehicle, in yet another embodiment at least about 5percent to about 60 percent by weight of the ink vehicle. Similarly,when present, urea, amide and imide derivatives of oxidized synthetic orpetroleum waxes may be present in an amount of from about 1 percent toabout 80 percent by weight of the ink vehicle, in another embodimentfrom about 3 percent to about 70 by weight of the ink vehicle, in yetanother embodiment at least about 5 percent to about 60 percent byweight of the ink vehicle.

Another type of ink vehicle may be n-paraffinic, branched paraffinic,and/or aromatic hydrocarbons, typically with from about 5 to about 100,such as from about 20 to about 180 or from about 30 to about 60 carbonatoms, generally prepared by the refinement of naturally occurringhydrocarbons, such as BE SQUARE 185 and BE SQUARE 195, with molecularweights (Mn) of from about 100 to about 5,000, such as from about 250 toabout 1,000 or from about 500 to about 800, for example such asavailable from Petrolite.

Highly branched hydrocarbons, typically prepared by olefinpolymerization, such as the VYBAR materials available from Petrolite,including VYBAR 253 (Mn=520), VYBAR 5013 (Mn=420), and the like, mayalso be used. In addition, the ink vehicle may be an ethoxylatedalcohol, such as available from Petrolite and of the general formula

wherein x is an integer of from about 1 to about 50, such as from about5 to about 40 or from about 11 to about 24 and y is an integer of fromabout 1 to about 70, such as from about 1 to about 50 or from about 1 toabout 40. The materials may have a melting point of from about 60° C. toabout 150° C., such as from about 70° C. to about 120° C. or from about80° C. to about 110° C. and a molecular weight (Mn) range of from about100 to about 5,000, such as from about 500 to about 3,000 or from about500 to about 2,500. Commercial examples include UNITHOX 420 (Mn=560),UNITHOX 450 (Mn=900), UNITHOX 480 (Mn=2,250), UNITHOX 520 (Mn=700),UNITHOX 550 (Mn=1,100), UNITHOX 720 (Mn=875), UNITHOX 750 (Mn=1,400),and the like. When present, highly branched hydrocarbons may be presentin an amount of from about 1 percent to about 80 percent by weight ofthe ink vehicle, in another embodiment from about 3 percent to about 70by weight of the ink vehicle, in yet another embodiment at least about 5percent to about 60 percent by weight of the ink vehicle.

As an additional example of highly branched hydrocarbons, mention may bemade of fatty amides, such as monoamides, tetra-amides, mixturesthereof, and the like. Suitable monoamides may have a melting point ofat least about 50° C., for example from about 50° C. to about 150° C.,although the melting point can be below this temperature. Specificexamples of suitable monoamides include, for example, primary monoamidesand secondary monoamides. Stearamide, such as KEMAMIDE S available fromWitco Chemical Company and CRODAMIDE S available from Croda,behenamide/arachidamide, such as KEMAMIDE B available from Witco andCRODAMIDE BR available from Croda, oleamide, such as KEMAMIDE Uavailable from Witco and CRODAMIDE OR available from Croda, technicalgrade oleamide, such as KEMAMIDE O available from Witco, CRODAMIDE Oavailable from Croda, and UNISLIP 1753 available from Uniqema, anderucamide such as KEMAMIDE E available from Witco and CRODAMIDE ERavailable from Croda, are some examples of suitable primary amides.Behenyl behenamide, such as KEMAMIDE EX666 available from Witco, stearylstearamide, such as KEMAMIDE S-180 and KEMAMIDE EX-672 available fromWitco, stearyl erucamide, such as KEMAMIDE E-180 available from Witcoand CRODAMIDE 212 available from Croda, erucyl erucamide, such asKEMAMIDE E-221 available from Witco, oleyl palmitamide, such as KEMAMIDEP-181 available from Witco and CRODAMIDE 203 available from Croda, anderucyl stearamide, such as KEMAMIDE S-221 available from Witco, are someexamples of suitable secondary amides. Additional suitable amidematerials include KEMAMIDE W40 (N,N′-ethylenebisstearamide), KEMAMIDEP181 (oleyl palmitamide), KEMAMIDE W45 (N,N′-thylenebisstearamide), andKEMAMIDE W20 (N,N′-ethylenebisoleamide).

High molecular weight linear alcohols, such as those available fromPetrolite and of the general formula

wherein x is an integer of from about 1 to about 50, such as from about5 to about 35 or from about 11 to about 23, may also be used as the inkvehicle. These materials may have a melting point of from about 50° C.to about 150° C., such as from about 70° C. to about 120° C. or fromabout 75° C. to about 110° C., and a molecular weight (Mn) range of fromabout 100 to about 5,000, such as from about 200 to about 2,500 or fromabout 300 to about 1,500. Commercial examples include the UNILINmaterials such as UNILIN 425 (Mn˜460), UNILIN 550 (Mn˜550), UNILIN 700(Mn˜700), and the like.

A still further example includes hydrocarbon-based waxes, such as thehomopolymers of polyethylene available from Petrolite and of the generalformula

wherein x is an integer of from about 1 to about 200, such as from about5 to about 150 or from about 12 to about 105. These materials may have amelting point of from about 60° C. to about 150° C., such as from about70° C. to about 140° C. or from about 80° C. to about 130° C. and amolecular weight (Mn) of from about 100 to about 5,000, such as fromabout 200 to about 4,000 or from about 400 to about 3,000. Example waxesinclude the line of waxes, such as POLYWAX 500 (Mn=500), POLYWAX 655(Mn=655), POLYWAX 850 (Mn=850), POLYWAX 1000 (Mn=1,000), and the like.

Another example includes modified maleic anhydride hydrocarbon adductsof polyolefins prepared by graft copolymerization, such as thoseavailable from Petrolite and of the general formulas

wherein R is an alkyl group with from about 1 to about 50, such as fromabout 5 to about 35 or from about 6 to about 28 carbon atoms, R¹ is anethyl group, a propyl group, an isopropyl group, a butyl group, anisobutyl group, or an alkyl group with from about 5 to about 500, suchas from about 10 to about 300 or from about 20 to about 200 carbonatoms, x is an integer of from about 9 to about 13, and y is an integerof from about 1 to about 50, such as from about 5 to about 25 or fromabout 9 to about 13, and having melting points of from about 50° C. toabout 150° C., such as from about 60° C. to about 120° C. or from about70° C. to about 100° C.; those available from Petrolite and of thegeneral formula

wherein x is an integer of from about 1 to about 50, such as from about5 to about 25 or from about 9 to about 13, y is 1 or 2, and z is aninteger of from about 1 to about 50, such as from about 5 to about 25 orfrom about 9 to about 13; and those available from Petrolite and of thegeneral formula

wherein R₁ and R₃ are hydrocarbon groups and R₂ is either of one of thegeneral formulas

or a mixture thereof, wherein R′ is an isopropyl group, which materialsmay have melting points of from about 70° C. to about 150° C., such asfrom about 80° C. to about 130° C. or from about 90° C. to about 125°C., with examples of modified maleic anhydride copolymers includingCERAMER 67 (Mn=655, Mw/Mn=1.1), CERAMER 1608 (Mn=700, Mw/Mn=1.7), andthe like.

Additional examples of suitable additional ink vehicle materials for thephase change inks include rosin esters, such as glyceryl abietate(KE-100®); polyamides; dimer acid amides; fatty acid amides, includingARAMID C; epoxy resins, such as EPOTUF 37001, available from RiecholdChemical Company; fluid paraffin waxes; fluid microcrystalline waxes;Fischer-Tropsch waxes; polyvinyl alcohol resins; polyols; celluloseesters; cellulose ethers; polyvinyl pyridine resins; fatty acids; fattyacid esters; poly sulfonamides, including KETJENFLEX MH and KETJENFLEXMS80; benzoate esters, such as BENZOFLEX S552, available from VelsicolChemical Company; phthalate plasticizers; citrate plasticizers; maleateplasticizers; polyvinyl pyrrolidinone copolymers; polyvinylpyrrolidone/polyvinyl acetate copolymers; novolac resins, such as DUREZ12 686, available from Occidental Chemical Company; and natural productwaxes, such as beeswax, montan wax, candelilla wax, GILSONITE (AmericanGilsonite Company), and the like; mixtures of linear primary alcoholswith linear long chain amides or fatty acid amides, such as those withfrom about 6 to about 24 carbon atoms, including PARICIN 9 (propyleneglycol monohydroxystearate), PARICIN 13 (glycerol monohydroxystearate),PARICIN 15 (ethylene glycol monohydroxystearate), PARICIN 220(N(2-hydroxyethyl)-12-hydroxystearamide), PARICIN 285(N,N-ethylene-bis-12-hydroxystearamide), FLEXRICIN 185(N,N′-ethylene-bis-ricinoleamide), and the like. Further, linear longchain sulfones with from about 4 to about 16 carbon atoms, such asdiphenyl sulfone, n-arnyl sulfone, n-propyl sulfone, n-pentyl sulfone,n-hexyl sulfone, n-heptyl sulfone, n-octyl sulfone, n-nonyl sulfone,n-decyl sulfone, n-undecyl sulfone, n-dodecyl sulfone, n-tridecylsulfone, n-tetradecyl sulfone, n-pentadecyl sulfone, n-hexadecylsulfone, chlorophenyl methyl sulfone, and the like, are suitable inkvehicle materials. These additional examples of suitable ink vehiclesmay be present in the ink vehicle in any suitable amount for examplefrom about 1 to about 90 weight percent of the ink vehicle, such as fromabout 5 to about 60 weight percent or from about 10 to about 30 weightpercent of the ink vehicle.

The ink vehicle may comprise one or more of the aforementioned suitablematerials. As used herein, “one or more” and “at least one” refers tofrom 1 to about 10, such as from 1 to about 8 or from 1 to about 5 ofany given feature disclosed herein.

The ink vehicle may comprise from about 25% to about 99.5% by weight ofthe ink, for example from about 30% to about 90% or from about 50% toabout 85% by weight of the ink.

The phase change inks also contain at least one colorant, for example,from 1 to about 10, such as from 1 to about 4 or from 1 to about 2colorants. The colorant is present in the ink in any desired amount,typically from about 0.5 to about 75 percent by weight of the inkvehicle, for example from about 1 to about 50 percent by weight of theink vehicle.

Examples of suitable colorants include pigments, dyes, mixtures ofpigments and dyes, mixtures of pigments, mixtures of dyes, and the like.Any dye or pigment may be chosen, provided that it is capable of beingdispersed or dissolved in the ink vehicle and is compatible with theother ink components.

Examples of suitable pigments include, for example, Violet PALIOGENViolet 5100 (BASF); PALIOGEN Violet 5890 (BASF); HELIOGEN Green L8730(BASF); LITHOL Scarlet D3700 (BASF); SUNFAST® Blue 15:4 (Sun Chemical249-0592); Hostaperm Blue B2G-D (Clariant); Permanent Red P-F7RK;Hostaperm Violet BL (Clariant); LITHOL Scarlet 4440 (BASF); Bon Red C(Dominion Color Company); ORACET Pink RF (Ciba); PALIOGEN Red 3871 K(BASF); SUNFAST® Blue 15:3 (Sun Chemical 249-1284); PALIOGEN Red 3340(BASF); SUNFAST® Carbazole Violet 23 (Sun Chemical 246-1670); LITHOLFast Scarlet L4300 (BASF); Sunbrite Yellow 17 (Sun Chemical 275-0023);HELIOGEN Blue L6900, L7020 (BASF); Sunbrite Yellow 74 (Sun Chemical272-0558); SPECTRA PAC® C Orange 16 (Sun Chemical 276-3016); HELIOGENBlue K6902, K6910 (BASF); SUNFAST® Magenta 122 (Sun Chemical 228-0013);HELIOGEN Blue D6840, D7080 (BASF); Sudan Blue OS (BASF); NEOPEN BlueFF4012 (BASF); PV Fast Blue B2GO1 (Clariant); IRGALITE Blue BCA (Ciba);PALIOGEN Blue 6470 (BASF); Sudan Orange G (Aldrich), Sudan Orange 220(BASF); PALIOGEN Orange 3040 (BASF); PALIOGEN Yellow 152, 1560 (BASF);LITHOL Fast Yellow 0991 K (BASF); PALIOTOL Yellow 1840 (BASF); NOVOPERMYellow FGL (Clariant); Lumogen Yellow D0790 (BASF); Suco-Yellow L1250(BASF); Suco-Yellow D1355 (BASF); Suco Fast Yellow D1355, D1351 (BASF);HOSTAPERM Pink E 02 (Clariant); Hansa Brilliant Yellow 5GX03 (Clariant);Permanent Yellow GRL 02 (Clariant); Permanent Rubine L6B 05 (Clariant);FANAL Pink D4830 (BASF); CINQUASIA Magenta (DU PONT), PALIOGEN BlackL0084 (BASF); Pigment Black K801 (BASF); and carbon blacks such as REGAL330™ (Cabot), Carbon Black 5250, Carbon Black 5750 (Columbia Chemical),mixtures thereof and the like.

Examples of suitable dyes include, for example, Usharect Blue 86 (DirectBlue 86), available from Ushanti Color; Intralite Turquoise 8GL (DirectBlue 86), available from Classic Dyestuffs; Chemictive Brilliant Red 7BH(Reactive Red 4), available from Chemiequip; Levafix Black EB, availablefrom Bayer; Reactron Red H8B (Reactive Red 31), available from AtlasDye-Chem; D&C Red #28 (Acid Red 92), available from Warner-Jenkinson;Direct Brilliant Pink B, available from Global Colors; Acid Tartrazine,available from Metrochem Industries; Cartasol Yellow 6GF Clariant; CartaBlue 2GL, available from Clariant; and the like.

In embodiments, solvent dyes may be utilized. Examples of solvent dyesinclude spirit soluble dyes which are compatible with the ink vehiclesdisclosed herein. Examples of suitable spirit solvent dyes includeNeozapon Red 492 (BASF); Orasol Red G (Ciba); Direct Brilliant Pink B(Global Colors); Aizen Spilon Red C-BH (Hodogaya Chemical); Kayanol Red3BL (Nippon Kayaku); Spirit Fast Yellow 3G; Aizen Spilon Yellow C-GNH(Hodogaya Chemical); Cartasol Brilliant Yellow 4GF (Clariant); PergasolYellow CGP (Ciba); Orasol Black RLP (Ciba); Savinyl Black RLS(Clariant); Morfast Black Conc. A (Rohm and Haas); Orasol Blue GN(Ciba); Savinyl Blue GLS (Sandoz); Luxol Fast Blue MBSN (Pylam); SevronBlue 5GMF (Classic Dyestuffs); Basacid Blue 750 (BASF), Neozapon BlackX51 [C.I. Solvent Black, C.I. 12195] (BASF), Sudan Blue 670 [C.I. 61554](BASF), Sudan Yellow 146 [C.I. 12700] (BASF), Sudan Red 462 C.I.[260501] (BASF) and the like. Other suitable colorants include non-polardyes, such as those disclosed in U.S. Pat. Nos. 6,472,523, 6,713,614,6,958,406, 6,998,493, 7,211,131 and 7,294,730, each of which isincorporated herein by reference in its entirety.

Examples of suitable propellants for the phase change inks include, forexample, water; hydrazine; alcohols such as ethanol, propanol, butanol,2,5-dimethyl-2,5-hexanediol, 3-hydroxy benzyl alcohol, and the like;cyclic amines and ureas, including 1,3-dimethyl urea such as imidazole,substituted imidazoles, including 2-imidazolidone, 2-ethyl imidazole,1,2,4-triazole, and the like; pyrazole and substituted pyrazoles,including 3,5-dimethylpyrazole and the like; pyrazine; carboxylic acids;sulfonic acids; aldehydes and ketones; hydrocarbons such as biphenyl,hexane, benzene; esters; phenols, including phenol, dichlorophenol,other halogen substituted phenols, and cresols; amides such aspropionamide, lactamide, and the like; imides; halocarbons; urethanes;ethers; sulfones, including dimethyl sulfone, methyl sulfone, diethylsulfone, and diphenyl sulfone; sulfamides such as methyl sulfamide;sulfonamides such as ortho, para-toluenesulfonamide, methyl sulfonamide,and the like; phosphites; phosphonates; phosphates; alkyl sulfides suchas methyl sulfide; alkyl acetates such as methyl acetate; sulfurdioxide; alkylene carbonates such as propylene carbonate; succinimide;and the like. Sulfones such as dimethyl sulfone, diethyl sulfone,diphenyl sulfone, and the like, and any mixtures thereof, may also beused.

The ink of embodiments may further include conventional additives totake advantage of the known functionality associated with suchconventional additives. Such additives may include, for example,biocides, defoamers, slip and leveling agents, plasticizers, pigmentdispersants, viscosity modifiers, antioxidants, absorbers, etc.

Optional biocides may be present in amounts of from about 0.1 to about1.0 percent by weight of the ink. Suitable biocides include, forexample, sorbic acid, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanechloride, commercially available as DOWICIL 200 (Dow Chemical Company),vinylene-bis thiocyanate, commercially available as CYTOX 3711 (AmericanCyanamid Company), disodium ethylenebis-dithiocarbamate, commerciallyavailable as DITHONE D14 (Rohm & Haas Company),bis(trichloromethyl)sulfone, commercially available as BIOCIDE N-1386(Stauffer Chemical Company), zinc pyridinethione, commercially availableas zinc omadine (Olin Corporation), 2-bromo-t-nitropropane-1,3-diol,commercially available as ONYXIDE 500 (Onyx Chemical Company), BOSQUATMB50 (Louza, Inc.), and the like. In addition, other optional additivessuch as dispersing agents or surfactants may be present in the inks,typically in amounts of from about 0.01 to about 20 percent by weight.Plasticizers that may be used include pentaerythritol tetrabenzoate,commercially available as BENZOFLEX 5552 (Velsicol ChemicalCorporation), trimethyl titrate, commercially available as CITROFLEX 1(Monflex Chemical Company), N,N-dimethyl oleamide, commerciallyavailable as HALCOMID M-18-OL (C. P. Hall Company), a benzyl phthalate,commercially available as SANTICIZER 278 (Ferro Corporation), and thelike, may be added to the ink vehicle, and may constitute from about 1to 100 percent of the ink vehicle component of the ink. Plasticizers caneither function as the ink vehicle or can act as an agent to providecompatibility between the ink propellant, which generally is polar, andthe ink vehicle, which generally is non-polar.

The viscosity modifier may be (1) 2-hydroxybenzyl alcohol, (2)4-hydroxybenzyl alcohol, (3) 4-nitrobenzyl alcohol, (4)4-hydroxy-3-methoxy benzyl alcohol, (5) 3-methoxy-4-nitrobenzyl alcohol,(6) 2-amino-5-chlorobenzyl alcohol, (7) 2-amino-5-methylbenzyl alcohol,(8) 3-amino-2-methylbenzyl alcohol, (9) 3-amino-4-methyl benzyl alcohol,(10) 2(2-(aminomethyl)phenylthio) benzyl alcohol, (11)2,4,6-trimethylbenzyl alcohol, (12) 2-amino-2-methyl-1,3-propanediol,(13) 2-amino-1-phenyl-1,3-propanediol, (14)2,2-dimethyl-1-phenyl-1,3-propanediol, (15)2-bromo-2-nitro-1,3-propanediol, (16) 3-tert-butylamino-1,2-propanediol,(17) 1,1-diphenyl-1,2-propanediol, (18) 1,4-dibromo-2,3-butanediol, (19)2,3-dibromo-1,4-butanediol, (20) 2,3-dibromo-2-butene-1,4-diol, (21)1,1,2-triphenyl-1,2-ethanediol, (22) 2-naphthalenemethanol, (23)2-methoxy-1-naphthalenemethanol, (24) decafluoro benzhydrol, (25)2-methylbenzhydrol, (26) 1-benzeneethanol, (27) 4,4′-isopropylidenebis(2-(2,6-dibromo phenoxy)ethanol), (28)2,2′-(1,4-phenylenedioxy)diethanol, (29)2,2-bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol, (30)di(trimethylolpropane), (31) 2-amino-3-phenyl-1-propanol, (32)tricyclohexylmethanol, (33) tris(hydroxymethyl)aminomethane succinate,(34) 4,4′-trimethylene bis(1-piperidine ethanol), (35) N-methylglucamine, (36) xylitol, or mixtures thereof. When present, theviscosity modifier is present in the ink in any effective amount, suchas from about 30 percent to about 55 percent by weight of the ink orfrom about 35 percent to about 50 percent by weight of the ink.

The optional antioxidants of the ink compositions protect the imagesfrom oxidation and also protect the ink components from oxidation duringthe heating portion of the ink preparation process. Specific examples ofsuitable antioxidants include NAUGUARD® 524, NAUGUARD® 76, and NAUGUARD®512 (commercially available from Uniroyal Chemical Company, Oxford,Conn.), IRGANOX® 1010 (a sterically hindered phenolic antioxidant havingthe formula

commercially available from Ciba Geigy), and the like. The antioxidant,when present, may be present in the ink in any desired or effectiveamount, such as from about 0.25 percent to about 10 percent by weight ofthe ink or from about 1 percent to about 5 percent by weight of the ink.

The ink can also optionally contain a UV absorber. The optional UVabsorbers primarily protect the generated images from UV degradation.Specific examples of suitable UV absorbers include (1)2-bromo-2′,4-dimethoxyacetophenone (Aldrich 19, 948-6), (2)2-bromo-2′,5′-dimethoxyacetophenone (Aldrich 10, 458-2), (3)2-bromo-3′-nitroacetophenone (Aldrich 34, 421-4), (4)2-bromo-4′-nitroacetophenone (Aldrich 24, 561-5), (5)3′,5′-diacetoxyacetophenone (Aldrich 11, 738-2), (6) 2-phenylsulfonylacetophenone (Aldrich 34, 150-3), (7) 3′-aminoacetophenone (Aldrich 13,935-1), (8) 4′-aminoacetophenone (Aldrich A3, 800-2), (9)1H-benzotriazole-1-acetonitrile (Aldrich 46, 752-9), (10)2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (Aldrich 42, 274-6),(11) 1,1-(1,2-ethane-diyl)bis(3,3,5,5-tetramethylpiperazinone)(commercially available from Goodrich Chemicals), (12)2,2,4-trimethyl-1,2-hydroquinoline (commercially available from MobayChemical), (13) 2-(4-benzoyl-3-hydroxy phenoxy)ethylacrylate, (14)2-dodecyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)succinimide(commercially available from Aldrich Chemical Co., Milwaukee, Wis.),(15)2,2,6,6-tetramethyl-4-piperidinyl/β-tetramethyl-3,9-(2,4,8,10-tetraoxospiro(5,5)-undecane) diethyl-1,2,3,4-butane tetracarboxylate(commercially available from Fairmount), (16)N-(p-ethoxycarbonylphenyl)-N′-ethyl-N′-phenylformadine (commerciallyavailable from Givaudan), (17)6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline (commercially availablefrom Monsanto Chemicals), (18)2,4,6-tris-(N-1,4-dimethylpentyl-4-phenylenediamino)-1,3,5-triazine(commercially available from Uniroyal), (19)2-dodecyl-N-(2,2,6,6-tetrame-thyl-4-piperidinyl)succinimide(commercially available from Aldrich Chemical Co.), (20)N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide(commercially available from Aldrich Chemical Co.), (21)(1,2,2,6,6-pentamethyl-4-piperidinyl/β-tetramethyl-3,9-(2,4,8,10-tetraoxo-spiro-(5,5)undecane)diethyl)-1,2,3,4-butane tetracarboxylate(commercially available from Fairmount), (22)(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate(commercially available from Fairmount), (23) nickel dibutyl dithiocarbamate (commercially available as UV-Chek AM-105 from Ferro), (24)2-amino-2′,5-dichlorobenzophenone (Aldrich 10,515-5), (25)2′-amino-4′,5′-dimethoxyacetophenone (Aldrich 32,922-3), (26)2-benzyl-2-(dimethylamino)-4′-morpholino butyrophenone (Aldrich40,564-7), (27) 4′-benzyloxy-2′-hydroxy-3′-methylacetophenone (Aldrich29,884-0), (28) 4,4′-bis(diethylamino)benzophenone (Aldrich 16,032-6),(29) 5-chloro-2-hydroxy benzophenone (Aldrich C4,470-2), (30)4′-piperazinoacetophenone (Aldrich 13,646-8), (31)4′-piperidinoacetophenone (Aldrich 11, 972-5), (32)2-amino-5-chlorobenzophenone (Aldrich A4,556-4), (33)3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole (Aldrich46,073-7), and the like, such as the UV absorbers described in U.S. Pat.No. 7,084,189, which is incorporated herein in its entirety byreference, as well as mixtures thereof. When present, the optional UVabsorber may be present in the ink in any desired or effective amount,such as from about 1 percent to about 10 percent by weight of the ink orfrom about 3 percent to about 5 percent by weight of the ink.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 100° C.,and in one embodiment of no more than about 140° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature. In a specific embodiment, during theformation process, the inks in their molten state are poured into moldsand then allowed to cool and solidify to form ink sticks of any desiredshape.

Printed images may be generated with the ink described herein byincorporating the ink into an ink jet device, for example a thermal inkjet device, an acoustic ink jet device or a piezoelectric ink jetdevice, and concurrently causing droplets of the molten ink to beejected in a pattern onto a substrate such as paper or transparencymaterial, which can be recognized as an image. The ink is typicallyincluded in the at least one reservoir connected by any suitable feedingdevice to the ejecting channels and orifices of the ink jet head forejecting the ink. In the jetting procedure, the ink jet head may beheated, by any suitable method, to the jetting temperature of the inks.The phase change inks are thus transformed from the solid state to amolten state for jetting. “At least one” or “one or more” as used todescribe components of the ink jet device, such as the ejectingchannels, orifices, etc., refers to from 1 to about 2 million, such asfrom about 1000 to about 1.5 million or about 10,000 to about 1 millionof any such component found in the ink jet device. “At least one” or“one or more” as used to describe other components of the ink jet devicesuch as the ink jet head, reservoir, feeder, etc., refers to from 1 toabout 15, such as from 1 to about 8 or from 1 to about 4 of any suchcomponent found in the ink jet device.

The inks can also be employed in indirect (offset) printing ink jetapplications, wherein when droplets of the melted ink are ejected in animagewise pattern onto a recording substrate, the recording substrate isan intermediate transfer member and the ink in the imagewise pattern issubsequently transferred from the intermediate transfer member to afinal recording substrate, such as paper or transparency.

Embodiments described above will now be further illustrated by way ofthe following examples.

Examples of Methyl Amides Derived from Hydroxyl Containing CarboxylicAcids Example 1

About 500 g of 12-hydroxystearic acid (available from Caschem) was addedto a 4 necked 1 L kettle having a heating mantle, nitrogen flow,distillation arm, mechanical Tru-Bore Stirrer, and thermocouple runningto a temperature controller unit from Watlow. The temperature was set atabout 120° C. and allowed to heat. After about 50 minutes, thetemperature had reached about 133° C. and all of the contents weremolten. The stirrer was turned on. The temperature was set at about 110°C., and the mantle was lowered to facilitate cooling. When thetemperature had reached about 106° C., the mantle was raised and theaddition of about 161.4 g of about 33% methylamine in ethyl alcohol(available from Aldrich) was initiated through a 250 mL addition funnel.Addition was completed in about 3 minutes, the temperature had droppedto about 95° C., and the initial distilled solvent collected by thedistillation arm was returned to kettle. The temperature was set atabout 180° C., and the mixture was allowed to heat while being stirredfor about 5 hours. The mixture was poured into an aluminum foil pan andallowed to cool. The viscosity of the tan waxy solid was about 20.2 cpsas measured by a Ferranti-Shirley cone-plate viscometer at about 135° C.

The methyl amide of Example 1 has the following formula:

Example 2

About 31.7 g of aleuritic acid (available from Sabinsa Corp) was addedto a 100 mL 1-necked 45/50 round bottom tube having a condenser, N₂blowing through top of condenser and Teflon coated magnet. The reactionflask was placed in about a 130° C. oil bath and stirring was initiated.After about 30 minutes, about 16.5 grams of about 33% methylaminesolution in ethanol (available from Aldrich Chemical Company) was added.The temperature of the oil bath was increased to about 150° C., andstirred at this temperature for about 1.5 hours. The condenser was thenreplaced with a distillation setup and a N₂ stream was introduced wherethe thermometer would be placed in the distillation head. The N₂ wasdistilled off the water while the reaction mixture was stirred at about150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C., and the reaction mixturewas stirred with N₂ distillation for about 1 hour after reaching thistemperature. The nitrogen inlet tube was then removed, and a vacuum wasintroduced to distill all unreacted volatiles out of the flask for about1 hour. The mixture was poured into aluminum pans and allowed to cool.The viscosity of the solid product was about 163.8 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The methyl amide of Example 2 has the following formula:

Characterization of Methyl Amides Derived from Hydroxyl ContainingCarboxylic Acids

The rheological measurements were performed on the RFS3 Fluids Rheometerin the dynamic mode, using the 50 mm cone and a gap of 53 microns. Thetest performed was a temperature step sweep from about 140° C. to about50° C. at a constant frequency of about 1 Hz. The methyl-amides derivedfrom the hydroxyl containing carboxylic acids do not display anycrystallinity due to their low molecular weight and the non-linearity ofthe 12-hydroxystearic and aleuritic acids, respectively. They have a lowviscosity in the melt, they are solids at about room temperature,approximately 25° C., due to the hydrogen bonding and at the same timethe hydroxyl functionality leads to increased hydrophilicity. Due tothese properties, these methyl amides may be utilized as replacementsfor KE100 resins in various ink formulations.

Examples of Methyl Amides Derived from Straight Chained Carboxylic AcidsExample 3

About 500 g of stearic acid (available from Aldrich) was added to a 4necked 1 L kettle with heating mantle, nitrogen flow, distillation arm,mechanical Tru-Bore Stirrer, and a thermocouple running to a temperaturecontroller unit from Watlow. The temperature was set at about 120° C.and allowed to heat. After about 25 minutes, the temperature had reachedabout 120° C. and all solids were molten. The stirrer was turned on. Thetemperature was set at about 110° C. and the mantle was lowered tofacilitate cooling. When the temperature had reached about 115° C., themantle was raised and the addition of about 169.7 g of about 33%methylamine in ethyl alcohol (available from Aldrich) was initiatedthrough a 250 mL addition funnel. Addition was completed in about 3minutes, the temperature had dropped to about 95° C., and the initialdistilled solvent collected by the distillation arm was returned to thekettle. Slight yellowing of the mixture was observed after addition ofthe methylamine. The temperature was set at about 180° C., and themixture was allowed to heat under stirring for about 5 hours. Themixture was poured into an aluminum foil pan and allowed to cool. Theviscosity of the tan waxy solid was about 1.02 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The methyl amide of Example 3 has the following formula:

where n is 1.

Example 4

About 500 g of UNICID 425 (available from Baker Petrolite) was added toa 4 necked 1 L kettle with heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and thermocouple running to atemperature controller unit from Watlow was charged. The temperature wasset at about 120° C. and allowed to heat. After about 40 minutes thetemperature had reached about 114° C. and all solids were molten. Thestirrer was turned on. Temperature was set at about 110° C. When thetemperature had reached about 114° C., the addition of about 84 g ofabout 33% methylamine in ethyl alcohol (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was complete inabout 3 minutes, the temperature had dropped to about 95° C., and theinitial distilled solvent collected by the distillation arm was returnedto kettle. The temperature was set at about 180° C. and the mixture wasallowed to heat under stirring for about 5 hours. The mixture was pouredinto an aluminum foil pan and allowed to cool. The viscosity of the tanwaxy solid was about 11.97 cps as measured by a Ferranti-Shirleycone-plate viscometer at about 135° C.

The methyl amide of Example 4 has the following formula:

where n is 6.

Example 5

About 500 g UNICID 550 (available from Baker Petrolite) was added to a 4necked 1 L kettle having a heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and thermocouple running to atemperature controller unit from Watlow. The temperature was set atabout 120° C. and allowed to heat. After about 65 minutes, thetemperature had reached about 127° C. and all solids were molten. Thestirrer was turned on. The temperature was set at about 110° C. Whentemperature had reached about 112° C., the addition of about 65.5 g ofabout 33% methylamine in ethyl alcohol (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was complete inabout 3 minutes, white solids observed at methylamine point of contact,and the initial distilled solvent collected by the distillation arm wasreturned to kettle. The temperature was set at about 180° C. and themixture was allowed to heat under stirring for about 5 hours. Mixturewas poured into an aluminum foil pan and allowed to cool. The viscosityof the tan waxy solid was about 9 cps as measured by a Ferranti-Shirleycone-plate viscometer at about 135° C.

The methyl amide of Example 5 has the following formula:

where n is 11.

Example 6

About 750 g UNICID 700 (available from Baker Petrolite) was added to a 4necked 1 L kettle having a heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and thermocouple running to atemperature controller unit from Watlow. The temperature was set atabout 120° C. and allowed to heat. After about 65 minutes, thetemperature had reached about 128° C. and all solids were molten. Thestirrer was turned on, and the temperature went to about 118° C. and theaddition of about 65.2 g of about 33% methylamine in ethyl alcohol(available from Aldrich) was initiated through a 250 mL addition funnel.Addition was complete in about 3 minutes, and white solids were observedat methylamine point of contact. The temperature was set at about 180°C. and the mixture was allowed to heat under stirring for about 5 hours.The mixture was poured into an aluminum foil pan and allowed to cool.The viscosity of the tan waxy solid was about 11.67 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The methyl amide of Example 6 has the following formula:

where n is 16.

Example 7

About 500 g UNICID 350 (available from Baker Petrolite) was added to a 4necked 1 L kettle having a heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and thermocouple running to atemperature controller unit from Watlow. The temperature was set atabout 120° C. and allowed to heat. After about 25 minutes, thetemperature had reached about 104° C. and all solids were molten. Thestirrer was turned on. The temperature was set at about 100° C. When thetemperature had reached about 104° C. the addition of about 65.5 g ofabout 33% methylamine in ethyl alcohol (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was complete inabout 3 minutes, and the temperature had dropped to about 95° C. Thetemperature was set at about 180° C., and the mixture was allowed toheat while being stirring for about 5 hours. The mixture was poured intoan aluminum foil pan and allowed to cool. The viscosity of the tan waxysolid was about 2.89 cps as measured by a Ferranti-Shirley cone-plateviscometer at about 135° C.

The methyl amide of Example 7 has the following formula:

where n is 3.

Example 8

About 500 g PRIFRAC 2989 behenic acid (available from Uniqema) was addedto a 4 necked 1 L kettle having a heating mantle, nitrogen flow,distillation arm, mechanical Tru-Bore Stirrer, and thermocouple runningto a temperature controller unit from Watlow. The temperature was set atabout 120° C. and allowed to heat. After about 15 minutes, thetemperature had reached about 104° C. and all solids were molten. Thestirrer was turned on. The temperature was set at about 100° C. When thetemperature had reached about 111° C., the addition of about 135.8 g ofabout 33% methylamine in ethyl alcohol (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was completed inabout 3 minutes, and the temperature had dropped to about 96° C. Slightyellowing of mixture was observed following addition of the methylamine.The temperature was set at about 180° C. and the mixture was allowed toheat under stirring for about 4 hours. The mixture was poured into analuminum foil pan and allowed to cool.

The methyl amide of Example 8 has the following formula:

where n is 3.Characterization of Methyl Amides Derived from Straight ChainedCarboxylic Acids

The rheological measurements were performed on an RFS3 Fluids Rheometeravailable from TA Instruments in the dynamic mode, using the 50 mm coneand a gap of 53 microns. The test performed was a temperature step sweepfrom about 140° C. to about 90° C. at a constant frequency of about 1Hz. From about 140° C. to a temperature slightly above the onset ofcrystallization temperature, about 5° C. decrements were used with anequilibration time of about 180 seconds at each temperature, followed byabout 2° C. steps to about 90° C. at about 120 seconds intervals todetermine the crystallization transition more accurately. Upon heating,about a 140° C. was achieved in about 5° C. steps to determine thetemperature when there is a complete re-melting of the crystallinestructure.

The viscosity at about 110° C. as well as at the onset ofcrystallization temperatures are a function of the chain length of thestarting acid used in the reaction. This enables the control of theviscosity and the onset of crystallization temperature of the final ink.The methyl-amide based on the shorter chain stearic acid (Example 3)could have a dual role; it could be a replacement for POLYWAX resinscurrently used in ink formulations because they have a similar viscositybut at the same time, the methyl-amide is a dye solubilizer and hassuperior miscibility with the other ink components. The othermethyl-amides derived from longer straight chained carboxylic acidscould be used as viscosity improvers and ink compatibilizers in variousink formulations.

Data for Examples 1-8 is demonstrated below in Table 1.

Peak Heat of Viscosity Viscosity Onset of Melting fusion Hardness @ 140°C. @ 110° C. crystallization (° C.) - (J/g) - (dmm at Example Type Acid(cps) (cps) (° C.) Rheology DSC DSC RT) 1 Methyl- 12-hydroxy- 18.5 27.638.0 N/A N/A — amine stearic acid 2 Methyl- aleuritic acid 130.1 448.245.0 N/A N/A — amine 3 Methyl- C18 - Stearic 3.2 5.7 64.0 65.5 189.0 7.5amine Acid 8 Methyl- C22 - Behenic 4.3 6.7 75.0 77.3 211.5 3.5 amineAcid 7 Methyl- C22 - UNICID 5.0 8.9 85.0 72.7 170.0 4.0 amine 350 4Methyl- C28 - UNICID 6.1 10.3 95.0 87.9 257.5 2.0 amine 425 5 Methyl-C38 - UNICID 8.2 15.7 99.0 101.8 236.1 1.0 amine 550 6 Methyl- C48 -UNICID 9.7 21.3 104.0 106.1 225.3 0.5 amine 700Examples of Methyl Amides Derived from Branched Carboxylic Acids

Example 9

About 500 g of isostearic acid (available as PRISORINE 3505 fromUniqema) was added to a 1000 mL 3-necked round bottom flask withcondenser in the middle neck, a glass stopper in each of the other 2outside necks, N₂ blowing through top of condenser, and with a Tefloncoated magnet. The reaction flask was placed in about a 110° C. oil bathand stirring was initiated. After about 5 minutes, about 165 grams ofabout 33% methyl amine (in about 67% ethanol available from AldrichChemical Company) was added slowly over about 15 minutes through thecondenser. The reaction mixture was allowed to stir for about 1 hour atabout 110° C. The oil bath temperature controller was then increased toabout 150° C. and the reaction mixture stirred for about 30 minutesafter reaching this temperature. The temperature controller was thenincreased to about 190° C. After about 2 hours at about 190° C., thecondenser was replaced with a glass stopper (in the middle neck), adistillation setup was attached to one of the outside necks, and a N₂stream attached to the other neck. The N₂ was distilled off the waterwhile the reaction mixture was stirred at about −190° C. for 2 abouthours. The product was poured into a glass jar and allowed to cool. Theviscosity of the viscous liquid was about 2.9 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The methyl amide of Example 9 has the following formula:

Example 10

About 60 g of ISOCARB 24 acid (available from Condea Vista Corp) wasadded to about a 100 mL 1-necked 45/50 round bottom tube with condenserand N2 blowing through the top of the condenser, and with a Tefloncoated magnet. The reaction flask was placed in about a 100° C. oil bathand stirring was initiated once all of the solid was melted. After about60 minutes, about 16 grams of a about 33% methylamine solution inethanol (available from Aldrich Chemical Company) was added. Thetemperature of the oil bath was increased to about 150° C. and stirredat this temperature for about 1.5 hours. The condenser was then replacedwith a distillation setup, which was distilled off the water while thereaction mixture stirred at about 150° C. for about an additional 2hours. The oil bath temperature controller was then increased to about190° C., and the reaction mixture was stirred with distillation forabout 1 hour after reaching this temperature. A nitrogen inlet tube wasthen placed subsurface and gentle N₂ bubbling was introduced to distillall unreacted volatiles out of the flask for about 1 hour. The mixturewas poured into aluminum pans and allowed to cool. The viscosity of thesolid product was about 3.34 cps as measured by a Ferranti-Shirleycone-plate viscometer at about 135° C.

The methyl amide of Example 10 has the following formula:

where n is 4.

Example 11

About 40 g of 2-ethylhexanoic acid (available from Aldrich ChemicalCorp) was added to about a 100 mL 1-necked 45/50 round bottom tube witha condenser and N₂ blowing through top of the condenser, and with Tefloncoated magnet. The reaction flask was placed in about a 120° C. oil bathand stirring was initiated. After about 160 minutes, about 27 grams ofabout 33% methylamine solution in ethanol (available from AldrichChemical Company) was added. The temperature of the oil bath wasincreased to about 150° C. and stirred at this temperature for about 1.5hours. The condenser was then replaced with a distillation setup, whichdistilled off the water while the reaction mixture was stirred at about150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred with distillation for about 1 hour after reaching thistemperature. A nitrogen inlet tube was then placed subsurface and gentleN₂ bubbling was introduced to distill all unreacted volatiles out of theflask for about 1 hour. The viscous liquid was poured into a jar andallowed to cool.

The methyl amide of Example 11 has the following formula:

where n is 0.Characterization of Methyl Amides Derived from Branched Carboxylic Acids

The use of branched carboxylic acids in the synthesis of methyl-amidesled to the formation of materials with a low viscosities and low degreesof crystallinity. As with other classes of materials, the chain lengthof the acid used has a major impact on the properties of the amides suchas mechanical properties and viscosity. The ones described in Examples 9and 11 are liquid at about room temperature, approximately 25° C., withviscosities at about 110° C. of about 5.5 cps and about 1.2 cps,respectively.

The methyl-amide with Isocarb 24 acid described in Example 10 had ahigher chain length and was a solid at about room temperature,approximately 25° C. It had a viscosity of about 5.0 cps at about 110°C. and an onset of crystallization temperature of about 55° C.

Examples of Di-Amides Derived from Branched Carboxylic Acids Example 12

About 100 g of isostearic acid (available as Prisorine 3505 fromUniqema) was added to a 1000 mL 3-necked round bottom flask having acondenser in the middle neck, a glass stopper in each of the other 2outside necks, N₂ blowing through top of condenser and a Teflon coatedmagnet. The reaction flask was placed in about a 120° C. oil bath andstirring was initiated. After about 5 minutes, about 19.7 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the side arms. The reaction mixture was stirredfor about 10 minutes at about 120° C. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred for about 1 hour after reaching this temperature. Thecondenser was then replaced with a glass stopper (in the middle neck), adistillation setup was attached to one of the outside necks and a N₂stream was attached to the other neck. The N₂ was distilled off thewater while the reaction mixture was stirred at about 190° C. for aboutan additional 2 hours. The reaction product was then poured intoaluminum tins and allowed to solidify.

The di-amide of Example 12 has the following formula:

Example 13

About 50 g of isostearic acid (available as Prisorine 3505 from Uniqema)and a Teflon coated magnet were added to a 100 mL 45/50 1-necked roundbottom tube. A 45/50 4-neck adaptor was then attached to the 45/50 tube.A condenser was placed in the middle neck, a N₂ inlet was placed in oneof the necks and a glass stopper was placed in each of the other 2necks. The reaction flask was placed in about a 120° C. oil bath andstirring was initiated. After about 1 hour, about 10.6 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper was replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to about190° C. and the reaction mixture was stirred for about 4 hours afterreaching this temperature. The product was then poured into aluminumtins. The viscosity of the solid product was about 20 cps as measured bya Ferranti-Shirley cone-plate viscometer at a temperature of about 135°C.

The di-amide of Example 13 has the following formula:

Example 14

About 50 g of C-32 Guerbet Acid (available as Isocarb 32 from CondeaVista) and a Teflon coated magnet were added to a 100 mL 45/50 1-neckedround bottom tube. A 45/50 4-neck adaptor was then attached to the 45/50tube. A condenser was placed in the middle neck, a N₂ inlet was placedin one of the necks and a glass stopper was placed in each of the other2 necks. The reaction flask was placed in about a 120° C. oil bath andstirring was initiated. After about 1 hour, about 5.5 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to atemperature of about 190° C. and the reaction mixture stirred for about4 hours after reaching this temperature. The product was then pouredinto aluminum tins.

The di-amide of Example 14 has the following formula:

where n is 5.

Example 15

About 50 g of C-24 Guerbet Acid (available as Isocarb 24 from CondeaVista) and a Teflon coated magnet were added to a 100 mL 45/50 1-neckedround bottom tube. A 45/50 4-neck adaptor was then attached to the 45/50tube. A condenser was placed in the middle neck, a N₂ inlet was placedin one of the necks and a glass stopper was placed in each of the other2 necks. The reaction flask was placed in about a 120° C. oil bath andstirring was initiated. After about 1 hour, about 7.7 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to about190° C. and the reaction mixture was stirred for about 4 hours afterreaching this temperature. The product was then poured into aluminumtins.

The di-amide of Example 15 has the following formula:

where n is 4.

Example 16

About 806 g of neooctanoic acid (available from Exxon Corp) was added Toa 100 mL 1-necked 45/50 round bottom tube having a condenser, N₂ blowingthrough the top of the condenser and a Teflon coated magnet. Thereaction flask was placed in about a 130° C. oil bath and stirring wasinitiated. After about 30 minutes, about 31.3 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added. The temperature of the oil bath was increased to about 150°C. and stirred at this temperature for about 1.5 hours. The condenserwas then replaced with a distillation setup and a N₂ stream wasintroduced where the thermometer would be placed in the distillationhead. The N₂ distilled off the water while the reaction mixture wasstirred at about 150° C. for about an additional 2 hours. The oil bathtemperature controller was then increased to about 190° C. and thereaction mixture was stirred with N₂ distillation for about 1 hour afterreaching this temperature. The nitrogen inlet tube was then removed anda vacuum was introduced to distill all unreacted volatiles out of theflask for about 1 hour. The mixture was poured into aluminum pans andallowed to cool.

The di-amide of Example 16 has the following formula:

Characterization of Di-Amides Derived from Branched Carboxylic Acids

Due to the non-linear molecular conformation of both thetrans-1,2-diaminocyclohexane as well as the branched carboxylic acid,these di-amides have unusual properties. While the crystalline fractioncontributes to a low viscosity (about 43 cps at a temperature of about120° C.), the amorphous chains inhibit the growth of the crystallinedomains. As a result, these types of di-amide materials display a highdegree of flexibility and transparency. They are also thermally stableand display excellent adhesion to substrates due to the high degree ofhydrogen bonding and their permanent flexibility. The onset ofcrystallization temperature can be tailored by the ratio betweenreaction components, such as the trans-1,2-diaminocyclohexane and thebranched carboxylic acid.

Examples of Di-Amides Derived from Hydroxyl Containing Carboxylic AcidsExample 17

About 200 g of 12-hydroxystearic acid (available from Caschem) was addedto a 1000 mL 3-necked round bottom flask with a condenser in the middleneck, a glass stopper in each of the other 2 outside necks, N₂ blowingthrough top of condenser and Teflon coated magnet. The reaction flaskwas placed in an about 110° C. oil bath and stirring was initiated.After about 30 minutes, about 38 grams of trans-1,2-diaminocyclohexane(available from Aldrich Chemical Company) was added through one of theside arms. The reaction mixture was allowed to stir for about 10 minutesat about 120° C. The oil bath temperature controller was then increasedto about 150° C. and the reaction mixture was stirred for about 1 hourafter reaching this temperature. The condenser was then replaced with aglass stopper (in the middle neck), a distillation setup was attached toone of the outside necks and a N₂ stream attached to the other neck. TheN₂ distilled off the water while the reaction mixture stirred at about150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred with N₂ distillation for about 1 hour after reaching thistemperature. The nitrogen inlet tube was then lowered so as to be belowthe surface of the stirring 190° C. reaction mixture and the N₂ allowedto distill all un-reacted volatiles out of the flask for about 1 hour.The mixture was poured into aluminum pans and allowed to cool. Theviscosity of the solid di-amide was about 26.5 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The di-amide of Example 17 has the following formula:

Example 18

About 50 g of aleuritic acid (available from Sabinsa Corp) was added toa 100 mL 1-necked 45/50 round bottom tube, with condenser and N₂ blowingthrough top of condenser, and with Teflon coated magnet. The reactionflask was placed in about a 130° C. oil bath and stirring was initiated.After about 30 minutes, about 9.5 grams of trans-1,2-diaminocyclohexane(available from Aldrich Chemical Company) was added. The temperature ofthe oil bath was increased to about 150° C. and stirred at thistemperature for 1.5 hours. The condenser was then replaced with adistillation setup and a N₂ stream was introduced where the thermometerwould be placed in the distillation head. The N₂ was distilled off thewater while the reaction mixture was stirred at about 150° C. for aboutan additional 2 hours. The oil bath temperature controller was thenincreased to about 190° C. and the reaction mixture was stirred with N₂distillation for about 1 hour after reaching this temperature. Thenitrogen inlet tube was then removed and a vacuum introduced to distillall un-reacted volatiles out of the flask for about 1 hour. The mixturewas poured into aluminum pans and allowed to cool. The viscosity of thesolid di-amide was about 53.5 cps as measured by a Ferranti-Shirleycone-plate viscometer at about 135° C.

The di-amide of Example 18 has the following formula:

Characterization of Di-Amides Derived from Hydroxyl ContainingCarboxylic Acids

The melt viscosities at about 140° C. were about 24 cps for the di-amidein Example 17 based on 12-hydroxystearic acid, and about 45 cps for theone in Example 18 based on aleuritic acid.

The use of OH-containing acids lead to materials that are virtuallyamorphous at about room temperature, approximately 25° C. The only proofof the slight crystallization was seen in the storage modulus G′ belowabout 70° C. for the resin of Example 18. Since these materials areamides, they are miscible with the other ink components. At the sametime, they contribute to the hydrophilicity of the ink leading to animproved adhesion to paper and writability on the ink layer. G′ isdefined as the part of the shear stress that is in phase with the shearstrain divided by the strain under sinusoidal deformation (elasticcomponent).

Examples of Di-Amides Derived from Straight Chained Carboxylic AcidsExample 19

About 60 g of UNICID 700 (available from Baker Petrolite) and a Tefloncoated magnet were added to a 100 mL 45/50 1-necked round bottom tube. A45/50 4-neck adaptor was then attached to the 45/50 tube. A condenserwas placed in the middle neck, a N₂ inlet was placed in one of the necksand a glass stopper was placed in each of the other 2 necks, Thereaction flask was placed in about a 120° C. oil bath and stirring wasinitiated. After about 1 hour, about 3.8 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper was replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to atemperature of about 190° C. and the reaction mixture was stirred forabout 4 hours after reaching this temperature. The product was thenpoured into aluminum tins. The viscosity of the solid product was about27 cps as measured by a Ferranti-Shirley cone-plate viscometer at atemperature of about 135° C.

The di-amide of Example 19 has the following formula:

where n is 16.

Example 20

About 55 g of UNICID 550 (available from Baker Petrolite) and a Tefloncoated magnet were added to a 100 mL 45/50 1-necked round bottom tube. A45/50 4-neck adaptor was then attached to the 45/50 tube. A condenserwas placed in the middle neck, a N₂ inlet was placed in one of the necksand a glass stopper was placed in each of the other 2 necks. Thereaction flask was placed in about a 120° C. oil bath and stirring wasinitiated. After about 1 hour, about 4.1 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper was replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to atemperature of about 190° C. and the reaction mixture was stirred forabout 4 hours after reaching this temperature. The product was thenpoured into aluminum tins. The viscosity of the solid product was about30 cps as measured by a Ferranti-Shirley cone-plate viscometer at atemperature of about 135° C.

The di-amide of Example 20 has the following formula:

where n is 11.

Example 21

About 55 g of UNICID 425 (available from Baker Petrolite) and a Tefloncoated magnet were added to a 100 mL 45/50 1-necked round bottom tube. A45/50 4-neck adaptor was then attached to the 45/50 tube. A condenserwas placed in the middle neck, a N₂ inlet was placed in one of the necksand a glass stopper was placed in each of the other 2 necks. Thereaction flask was placed in about a 120° C. oil bath and stirring wasinitiated. After about 1 hour, about 5.3 grams oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to atemperature of about 190° C. and the reaction mixture stirred for about4 hours after reaching this temperature. The product was then pouredinto aluminum tins. The viscosity of the solid product was about 16.5cps as measured by a Ferranti-Shirley cone-plate viscometer at atemperature of about 135° C.

The di-amide of Example 21 has the following formula:

where n is 6.Characterization of Di-Amides Derived from Straight Chained CarboxylicAcids

The rheological measurements of Examples 19 through 21 were performed ona RFS3 Fluids Rheometer in the dynamic mode, using the 50 mm cone and agap of 53 microns. The test performed was a temperature step sweep fromabout 140° C. to about 90° C. at a constant frequency of about 1 Hz.From about 140° C. to a temperature slightly above the onset ofcrystallization temperature, 5° C. decrements were used with anequilibration time of about 180 seconds at each temperature, followed byabout 2° C. steps to about 90° C. at about 120 seconds intervals todetermine the crystallization transition more accurately. Upon heating,5° C. steps were used to obtain a temperature of about 140° C. todetermine the temperature when there is a complete re-melting of thecrystalline structure.

The viscosity at about 140° C. and the onset of crystallizationtemperatures are a function of the chain length of the starting acidused in the reaction. Due to their molecular conformation and possiblytheir ability to form hydrogen bonds, the di-amide materials of Examples19-21 have a relatively high onset of crystallization temperature ofover 110° C. However, due to their hardness, this class of materials maybe used as ink vehicle components to improve ink robustness.

Examples Tetra-Amides Derived from Straight Chained Carboxylic AcidsExample 22

About 511.8 g of UNICID 700 (available from Baker Petrolite) and about158.8 grams of PRIPOL 1006 Dimer Acid (available from Uniqema) wereadded to a 4 necked 1 L kettle having heating mantle, nitrogen flow,distillation arm, mechanical Tru-Bore Stirrer, and thermocouple runningto a temperature controller unit available from Watlow. The temperaturewas set at about 120° C. and heated. After the temperature had reachedabout 130° C. and all solids were molten, the stirrer was turned on andthe temperature was dropped to about 120° C. The addition of about 56.5grams of trans-1,2-diaminocyclohexane (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was completed inabout 3 minutes. The temperature was set at about 180° C. and themixture was heated while being stirred for about 5 hours. The mixturewas poured into an aluminum foil pan and allowed to cool. The viscosityof the tan waxy solid was about 70.0 cps as measured by aFerranti-Shirley cone-plate viscometer at a temperature of about 135° C.

The tetra-amide of Example 22 has the following formula:

where n is 16.

Example 23

About 404.4 g UNICID 550 (available from Baker Petrolite) and about158.5 grams of PRIPOL 1006 Dimer Acid (available from Uniqema) wereadded to a 4 necked 1 L kettle having a heating mantle, nitrogen flow,distillation arm, mechanical Tru-Bore Stirrer, and thermocouple runningto a temperature controller unit available from Watlow. The temperaturewas set at about 120° C. and heated. After the temperature had reachedabout 130° C. and all solids were molten, the stirrer was turned on andthe temperature dropped to about 120° C. The addition of about 56.5grams of trans-1,2-diaminocyclohexane (available from Aldrich) wasinitiated through a 250 mL addition funnel. Addition was completed inabout 3 minutes. The temperature was set at about 180° C. and themixture was allowed to heat while being stirred for about 5 hours. Themixture was poured into an aluminum foil pan and allowed to cool. Theviscosity of the tan waxy solid was about 76.5 cps as measured by aFerranti-Shirley cone-plate viscometer at a temperature of about 135° C.

The tetra-amide of Example 23 has the following formula:

where n is 11.

Example 24

About 208.1 g of UNICID 550 (available from Baker Petrolite) and about100 g of EMPOL 1008 Dimer Acid (available from Cognis) were added to a1000 mL 3-necked round bottom flask having a condenser in the middleneck, a glass stopper in each of the other 2 outside necks, N₂ blowingthrough top of condenser and a Teflon coated magnet. The reaction flaskwas placed in about a 130° C. oil bath until the contents were molten(this took about 1 hour) and then stirring was initiated. About 40.1 gof trans-1,2-diaminocyclohexane (available from Aldrich ChemicalCompany) was added through one of the side arms. The oil bathtemperature controller was then increased to about 150° C. and thereaction mixture was stirred for about 1 hour after reaching thistemperature. The condenser was then replaced with a glass stopper (inthe middle neck), a distillation setup was attached to one of theoutside necks, and a N₂ stream attached to the other neck. The N₂ wasdistilled off the water while the reaction mixture was stirred at about150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred for about 1 hour, with the N₂ distillation setup afterreaching this temperature. The reaction product was then poured intoaluminum tins and allowed to solidify. The viscosity of the viscousliquid was about 74.0 cps as measured by a Ferranti-Shirley cone-plateviscometer at a temperature of about 135° C.

The tetra-amide of Example 24 has the following formula:

where n is 11.

Example 25

About 301.8 g of UNICID 425 (available Baker Petrolite) and about 158.8g of PRIPOL 1006 Dimer Acid (available from Uniqema) were added to a 4necked 1 L kettle having a heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and a thermocouple running to atemperature controller unit available from Watlow. The temperature wasset at about 120° C. and allowed to heat. After the temperature hadreached about 130° C. and all solids were molten, the stirrer was turnedon and the temperature was dropped to about 120° C. The addition ofabout 57 grams of trans-1,2-diaminocyclohexane (available from Aldrich)was initiated through a 250 mL addition funnel. Addition was completedin about 3 minutes. The temperature was set at about 180° C. and themixture was allowed to heat while being stirred for about 5 hours. Themixture was poured into an aluminum foil pan and allowed to cool. Theviscosity of the tan waxy solid was about 88.7 cps as measured by aFerranti-Shirley cone-plate viscometer at a temperature of about 135° C.

The tetra-amide of Example 25 has the following formula:

where n is 6.

Example 26

About 389.6 g of UNICID 350 (available Baker Petrolite) and about 250.0g of PRIPOL 1006 Dimer Acid (available from Uniqema) were added to a 4necked 1 L kettle having a heating mantle, nitrogen flow, distillationarm, mechanical Tru-Bore Stirrer, and a thermocouple running to atemperature controller unit available from Watlow. The temperature wasset at about 120° C. and allowed to heat. After the temperature hadreached about 130° C. and all solids were molten, the stirrer was turnedon and the temperature was dropped to about 120° C. The addition ofabout 99.1 grams of trans-1,2-diaminocyclohexane (available fromAldrich) was initiated through a 250 mL addition funnel. Addition wascompleted in about 3 minutes. The temperature was set at about 180° C.and the mixture was allowed to heat while being stirred for about 5hours. The mixture was poured into an aluminum foil pan and allowed tocool.

The tetra-amide of Example 26 has the following formula:

where n is 3.

Example 27

About 176.5 g of behenic acid (available as Prifrac 2989 from Uniqema)and about 158.8 grams of PRIPOL 1006 Dimer Acid (available from Uniqema)were added to a 4 necked 1 L kettle having a heating mantle, nitrogenflow, distillation arm, mechanical Tru-Bore Stirrer, and a thermocouplerunning to a temperature controller unit available from Watlow. Thetemperature was set at about 120° C. and allowed to heat. After thetemperature had reached about 130° C. and all solids were molten, thestirrer was turned on and the temperature was dropped to about 120° C.The addition of about 57 g of trans-1,2-diaminocyclohexane (availablefrom Aldrich) was initiated through a 250 mL addition funnel. Additionwas completed in about 3 minutes. The temperature was set at about 180°C. and the mixture was allowed to heat while being stirred for about 5hours. The mixture was poured into an aluminum foil pan and allowed tocool. The viscosity of the tan waxy solid was about 950 cps as measuredby a Ferranti-Shirley cone-plate viscometer at a temperature of about135° C.

The tetra-amide of Example 26 has the following formula:

where n is 3.

Example 28

About 145.4 g of stearic acid (available from Aldrich Chemical Corp) andabout 158.5 grams of PRIPOL 1006 Dimer Acid (available from Uniqema)were added to a 4 necked 1 L kettle having a heating mantle, nitrogenflow, distillation arm, mechanical Tru-Bore Stirrer, and a thermocouplerunning to a temperature controller unit available from Watlow. Thetemperature was set at about 120° C. and allowed to heat. After thetemperature had reached about 130° C. and all solids were molten, thestirrer was turned on and the temperature was dropped to about 120° C.The addition of about 57 g of trans-1,2-diaminocyclohexane (availablefrom Aldrich) was initiated through a 250 mL addition funnel. Additionwas completed in about 3 minutes. The temperature was set at about 180°C. and the mixture was allowed to heat while being stirred for about 5hours. The mixture was poured into an aluminum foil pan and allowed tocool.

The tetra-amide of Example 28 has the following formula:

where n is 0.Characterization of Tetra-Amides Derived from Straight ChainedCarboxylic Acids

These tetra-amide materials cover an entire range of properties,depending on the chain length of the straight chain carboxylic acidused, as seen in Table 2 below.

Tetra-amide Derived From Onset of a Straight Viscosity Viscositycrystalli- Chained @ @ zation Heat of Carboxylic 140° C. 110° C. (°C.) - Fusion Example Acid (cps) (cps) Rheology (J/g) 22 Unicid 700 59.6186 96 154 23 Unicid 550 61.3 234.7 92 133 24 Unicid 550 67.8 309.1 103128 25 Unicid 425 70.3 308.7 94 91.3 26 Unicid 350 77.5 372.3 98 19.3 27Behenic Acid 127.3 1930.5 115 19.3 28 Stearic Acid 172.3 240000 120 14.9

The UNICID 550 of Examples 23 and 24 provide slightly different resultsbecause of stoichiometric differences between the two UNICID's obtainedfrom different manufacturers.

All the tetra-amide materials set forth in Table 2 above are hard atabout room temperature, approximately 25° C. The tetra-amides withlonger chains are highly crystalline, have a lower melt viscosity andare more opaque. The tetra-amides with shorter chains are moreamorphous, have higher viscosities and at the same time have improvedtransparency.

Examples Tetra-Amides Derived from Hydroxyl Containing Carboxylic AcidsExample 29

About 102 grams of 12-hydroxystearic acid (available from Caschem) andabout 105.5 g PRIPOL 1006 Dimer Acid were added to a 4 necked 1 L kettlehaving a heating mantle, nitrogen flow, distillation arm, mechanicalTru-Bore Stirrer, and a thermocouple running to a temperature controllerunit. The temperature was set at about 120° C. and allowed to heat.After about 50 minutes, the temperature had reached about 133° C. andall contents were molten. The stirrer was turned on. The temperature wasset at about 110° C. and the mantle was lowered to facilitate cooling.When the temperature had reached about 106° C. the mantle was raised andabout 57 grams of trans-1,2-diaminocyclohexane (available from Aldrich)was added through a 250 mL addition funnel. The addition was completedin about 3 minutes. The temperature was set at about 180° C. and themixture was allowed to heat while being stirred for about 5 hours. Themixture was poured into an aluminum foil pan and allowed to cool andsolidify.

The tetra-amide of Example 29 has the following formula:

Example 30

About 166 g of 12-hydroxystearic acid (available from Caschem) and about150 g of EMPOL 1008 Dimer Acid (available from Cognis) were added to a1000 mL 3-necked round bottom flask having a condenser in the middleneck, a glass stopper in each of the other 2 outside necks, N₂ blowingthrough the top of the condenser and a Teflon coated magnet. Thereaction flask was placed in about a 120° C. oil bath and stirring wasinitiated. After about 5 minutes, about 60 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the side arms. The reaction mixture stirred forabout 10 minutes at about 120° C. The oil bath temperature controllerwas then increased to a temperature of about 150° C. and the reactionmixture was stirred for about 1 hour after reaching this temperature.The condenser was then replaced with a glass stopper (in the middleneck), a distillation setup was attached to one of the outside necks anda N₂ stream was attached to the other neck. The N₂ was distilled off thewater while the reaction mixture was stirred at about 150° C. for aboutan additional 2 hours. The oil bath temperature controller was thenincreased to about 190° C. and the reaction mixture stirred for about 1hour with N₂ stream. After reaching this temperature, the reactionproduct was then poured into aluminum tins and allowed to solidify. Theviscosity of the viscous liquid was about 162.9 cps as measured by aFerranti-Shirley cone-plate viscometer at about 135° C.

The tetra-amide of Example 30 has the following formula:

Example 31

About 31.7 g of aleuritic acid (available from Sabinsa Corp) and about30 g of Empol 1008 Dimer Acid (available from Cognis) were added to a100 mL 1-necked 45/50 round bottom tube having a condenser, N₂ blowingthrough the top of the condenser and a Teflon coated magnet. Thereaction flask was placed in about a 130° C. oil bath and stirring wasinitiated. After about 30 minutes, about 12 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added. The temperature of the oil bath was increased to about 150°C. and stirred at this temperature for about 1.5 hours. The condenserwas then replaced with a distillation setup and N₂ stream was introducedwhere the thermometer would be placed in the distillation head. The N₂was distilled off the water while the reaction mixture was stirred atabout 150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred with N₂ distillation for about 1 hour after reaching thistemperature. The nitrogen inlet tube was then removed and a vacuum wasintroduced to distill all unreacted volatiles out of the flask for about1 hour. The mixture was poured into aluminum pans and allowed to cool.The viscosity of the solid di-amide was about 663.65 cps as measured bya Ferranti-Shirley cone-plate viscometer at about 135° C.

The tetra-amide of Example 31 has the following formula:

Characterization of Tetra-Amides Derived from Hydroxyl ContainingCarboxylic Acids

The properties of the materials that are described in the precedingexamples depend on the type of hydroxyl containing carboxylic acidsused. In Examples 27 and 28, 12-hydroxystearic acid was employed. BothExamples 26 and 27 have identical thermal and rheological properties.Their viscosities were about 160 cps at a temperature of about 140° C.,and had an onset of crystallization temperature of about 80° C. BothExamples 26 and 27 were transparent at about room temperature,approximately 25° C.

The molecular conformation of the aleuritic acid used Example 28inhibited the crystallization of the material. At about 140° C., it hada viscosity of about 650 cps. This particular tetra-amide of Example 28was mostly amorphous and did not show any crystallization behavior at atemperature as low as about 60° C. This material was very hard andtransparent at about room temperature, approximately 25° C., and couldbe used as a replacement for the KE100 resin, which is much more brittleand has a viscosity of about 4000 cps at a temperature of about 140° C.

Examples Tetra-Amides Derived from Branched Carboxylic Acids Example 32

About 25 g PRIPOL 1006 dimer acid (available from Uniqema) and about24.6 g of isostearic acid (available as Prisorine 3505 from Uniqema)were added to a 100 mL 45/50 1-necked round bottom tube having a Tefloncoated magnet. A 45/50 4-neck adaptor was then attached to the 45/50tube. A condenser was placed in the middle neck, a N₂ inlet was placedin one of the necks and a glass stopper was placed in each of the other2 necks. The reaction flask was placed in about a 120° C. oil bath andstirring was initiated. After about 1 hour, about 9.9 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the necks and the stopper was replaced. Thereaction mixture was stirred for about 1 hour at a temperature of about120° C. The oil bath temperature controller was then increased to about190° C. and the reaction mixture was stirred for about 4 hours afterreaching this temperature. The product was then poured into aluminumtins. The viscosity of the solid product was about 238.5 cps as measuredby a Ferranti-Shirley cone-plate viscometer at a temperature of about135° C.

The tetra-amide of Example 32 has the following formula:

Example 33

About 152.4 g isostearic acid (available as Prisorine 3505 from Uniqema)and about 150 g EMPOL 1008 Dimer Acid (available from Cognis) were addedto a 1000 mL 3-necked round bottom flask having a condenser in themiddle neck, a glass stopper in each of the other 2 outside necks, N₂blowing through the top of the condenser and a Teflon coated magnet. Thereaction flask was placed in about a 120° C. oil bath and stirring wasinitiated. After about 5 minutes, about 60 g oftrans-1,2-diaminocyclohexane (available from Aldrich Chemical Company)was added through one of the side arms. The reaction mixture was stirredfor about 10 minutes at a temperature of about 120° C. The oil bathtemperature controller was then increased to about 190° C. and thereaction mixture was stirred for about 1 hour after reaching thistemperature. The condenser was then replaced with a glass stopper (inthe middle neck), a distillation setup was attached to one of theoutside necks and a N₂ stream was attached to the other neck. The N₂ wasdistilled off the water while the reaction mixture was stirred at about190° C. for about an additional 2 hours. The reaction product was thenpoured into aluminum tins and allowed to solidify. The viscosity of theviscous liquid was about 229.9 cps as measured by a Ferranti-Shirleycone-plate viscometer at a temperature of about 135° C.

The tetra-amide of Example 33 has the following formula:

Example 34

About 25.6 g neooctanoic acid (available from Exxon Corp.) and about 50g of EMPOL 1008 Dimer Acid (available from Cognis) were added to a 100mL 1-necked 45/50 round bottom tube having condenser, N₂ blowing throughthe top of the condenser and a Teflon coated magnet. The reaction flaskwas placed in about a 130° C. oil bath and stirring was initiated. Afterabout 30 minutes, about 20 g of trans-1,2-diaminocyclohexane (availablefrom Aldrich Chemical Company) was added. The temperature of the oilbath was increased to about 150° C. and stirred at this temperature forabout 1.5 hours. The condenser was then replaced with a distillationsetup, and a N₂ stream was introduced where the thermometer would beplaced in the distillation head. The N₂ was distilled off the waterwhile the reaction mixture was stirred at a temperature of about 150° C.for about an additional 2 hours. The oil bath temperature controller wasthen increased to a temperature of about 190° C. and the reactionmixture was stirred with N₂ distillation for about 1 hour after reachingthis temperature. The nitrogen inlet tube was then removed and a vacuumwas introduced to distill all unreacted volatiles out of the flask forabout 1 hour. The mixture was poured into aluminum pans and allowed tocool. The viscosity of the solid product was about 201.6 cps as measuredby a Ferranti-Shirley cone-plate viscometer at a temperature of about135° C.

The tetra-amide of Example 34 has the following formula:

Characterization of Tetra-Amides Derived from Branched Carboxylic Acids

The use of 1,2-trans-diaminocyclohexane in the synthesis of tetra-amidesleads to materials that have a higher amorphous component and as aresult, they are hard and transparent. The use of branched carboxylicacids contributes even more to a disruption of the chain linearity andleads to materials that range from semicrystalline to amorphous. Theyhave lower melting transitions as well as improved toughness. Thematerials from Examples 31 and 32 maintain their semicrystallinebehavior, and have a viscosity of about 175 cps at a temperature ofabout 140° C., and a viscosity of about 1,200 cps at a temperature ofabout 110° C.

The neooctanoic acid used in Example 33 leads to a material with an evenhigher degree of amorphous content. The material of Example 33 is alsohard at about room temperature, approximately 25° C., has a viscosity ofabout 410 cps at a temperature of about 110° C. and does not display anychange in complex viscosity at a temperature as low as about 40° C.

For current ink formulations, these tetra-amide materials derived frombranched carboxylic acids could completely or partially replace knowntetra-amides, known triamides, and amorphous resins, such as KE100resin.

It is believed that the lower degree of crystallinity of the thistetra-amide materials leads to improved miscibility with the other inkcomponents, especially with amorphous resins, KE100 resin, as well asimproved robustness.

Examples Tetra-Amides Derived from a Dimer Acid, an Alkylene Diamine anda Carboxylic Acid Example 35

About 100 g of EMPOL 1008 dimer acid (available from Uniqema) and about101.5 g isostearic acid (available as Prisorine 3505 from Uniqema) wereadded to a 1000 mL 3-necked round bottom flask having a condenser in themiddle neck, a glass stopper in each of the other 2 outside necks, N₂blowing through top of condenser and Teflon coated magnet. The reactionflask was placed in about a 120° C. oil bath and stirring was initiated.After about 20 minutes, about 21.1 grams of ethylene diamine (availablefrom Aldrich Chemical Company) was quickly added through one of theoutside necks and the stopper was replaced. The oil bath temperaturecontroller was then increased to about 180° C. and the reaction mixturewas stirred for about 90 minutes after reaching this temperature. Thecondenser was then replaced with a glass stopper (in the middle neck), adistillation setup was attached to one of the outside necks and a N₂stream was attached to the other neck. The N₂ was distilled off thewater while the reaction mixture was stirred at about 180° C. for about2 hours. The temperature was then increased to about 180° C., and thereaction mixture was stirred with the N₂ distillation. All unreactedvolatiles were distilled out of the flask for about 1 hour. The productwas poured into aluminum pans and allowed to cool. The viscosity of thesolid tetra-amide was about 144 cps as measured by a Ferranti-Shirleycone-plate viscometer at about 110° C.

The tetra-amide of Example 35 has the following formula:

where R is ethylene.

Example 36

About 25.4 g of isostearic acid (available as PRISORINE 3505 fromUniqima) and about 25 g EMPOL 1008 Dimer Acid (available from Cognis)was added to a 100 mL 1-necked 45/50 round bottom tube having acondenser, N₂ blowing through the top of condenser and a Teflon coatedmagnet. The reaction flask was placed in about a 130° C. oil bath andstirring was initiated. After about 30 minutes, about 35.1 g ofJEFFAMINE D-400 (available from the Texaco Chemical Company) was added.The temperature of the oil bath was increased to about 150° C. andstirred at this temperature for about 1.5 hours. The condenser was thenreplaced with a distillation setup and a N₂ stream was introduced wherethe thermometer would be placed in the distillation head. The N₂ wasdistilled off the water while the reaction mixture was stirred at about150° C. for about an additional 2 hours. The oil bath temperaturecontroller was then increased to about 190° C. and the reaction mixturewas stirred with N₂ distillation for about 1 hour after reaching thistemperature. The nitrogen inlet tube was then removed and a vacuumintroduced to distill all unreacted volatiles out of the flask for about1 hour. The mixture was poured into aluminum pans and allowed to cool.

The tetra-amide of Example 36 has the following formula:

where R is

Characterization of Tetra-Amide Derived from a Dimer Acid, and AlkyleneDiamine and a Carboxylic Acid

The change in the molecular conformation from straight chain stearicacid to non-linear isostearic acid leads to dramatically improvedproperties for ink applications. As a comparison, the properties of aknown tetra-amide Comparative Example 1 is also presented in Table 3below.

The presence of a carboxylic acid having seventeen carbon atoms in thesynthesis of tetra-amides leads to materials with a higher concentrationof amorphous content and a lower degree of crystallinity. The higheramorphous/crystalline ratio will also inhibit the growth of thecrystalline fraction. These properties lead to the formation of a toughand transparent material. However, the molecular conformation of theisostearic acid based tetra-amide leads to a material with lower thermaltransitions, the onset of crystallization occurring at a temperature ofabout 92° C. compared to 126° C. for Comparative Example 2.

TABLE 3 Onset of Tetra- Viscosity Viscosity crystalli- Heat amide- @ @zation of straight 140° C. 110° C. (° C.) - Fusion Example chain table(cps) (cps) Rheology (J/g) Comparative Unicid 700 63.5 2052 118 141.5Example 1 Comparative Stearic Acid 87.3 5.9 × 10⁶ 126 47.3 Example 2Example 35 Isostearic 89.1  325 93 15.5 Acid

A tetra-amide derived from a dimer acid, and alkylene diamine and acarboxylic acid could be a replacement for the known tetra-amides andtri-amides, in addition to amorphous resins found in ink formulations,such as Resin 34 and KE100.

It is believed that the lower degree of crystallinity of thetetra-amides derived from a dimer acid, and alkylene diamine and acarboxylic acid will lead to improved miscibility with the other inkcomponents, especially with the amorphous resins, such as Resin 34 orKE100, as well improved robustness of the ink.

The lower crystallization temperature of this tetra-amide (about 90° C.)is approximately the same as other crystalline ink components andtherefore will contribute to a more homogeneous ink uponcrystallization.

Ink Examples Including Amides Described Herein

Preparation of Ink Example A with Methyl Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 43.79 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃); about 19.38        parts by weight of a methyl amide based on Unicid 425 (obtained        from Baker Petrolite and described in Example 4);    -   about 12.4 parts by weight tetra-amide resin obtained from the        reaction of one equivalent of a C-36 dimer acid (obtained from        Uniqema, New Castle, Del.) with two equivalents of ethylene        diamine and UNICID® 700 (obtained from Baker Petrolite), a long        chain hydrocarbon having a terminal carboxylic acid group,        prepared as described in Example 1 of U.S. Pat. No. 6,174,937,        which is incorporated by reference herein in its entirety;    -   about 1.83 parts by weight urethane resin obtained from the        reaction of two equivalents of ABITOL® E hydroabietyl alcohol        (obtained from Hercules Inc.) and one equivalent of isophorone        diisocyanate, prepared as described in Example 1 of U.S. Pat.        No. 5,782,966, which is incorporated by reference herein in its        entirety;    -   about 6.48 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453, which is incorporated by reference herein in its        entirety;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839, which is incorporated by reference herein in        its entirety.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 10.86 cps atabout 140° C.

Preparation of Ink Example B with Methyl Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 43.79 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 19.38 parts by weight of an methyl amide based on UNICID®        350 (obtained from Baker Petrolite and described in Example 4);    -   about 12.4 parts by weight tetra-amide resin obtained from the        reaction of one equivalent of a C-36 dimer acid (obtained from        Uniqema, New Castle, Del.) with two equivalents of ethylene        diamine and UNICID® 700 (obtained from Baker Petrolite), a long        chain hydrocarbon having a terminal carboxylic acid group,        prepared as described in Example 1 of U.S. Pat. No. 6,174,937;    -   about 11.83 parts by weight urethane resin obtained from the        reaction of two equivalents of ABITOL® E hydroabietyl alcohol        (obtained from Hercules Inc.) and one equivalent of isophorone        diisocyanate, prepared as described in Example 1 of U.S. Pat.        No. 5,782,966;    -   about 6.48 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical;    -   about 5.92 parts of a cyan dye as described in example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 10.47 cps atabout 140° C.

Preparation of Ink Example C with Methyl Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 46.25 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 19.08 parts by weight of an methyl amide based on UNICID®        425 (obtained from Baker Petrolite) and described in Example 4);    -   about 17.13 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 11.62 parts by weight KE100;    -   about 2.17 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523, which is incorporated by reference        herein in its entirety.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after 6 hours. The ink base was pouredinto molds containing about 31 grams of the colorless ink base andallowed to cool. The viscosity was about 10.85 cps and about 110° C.

Preparation of Ink Example D with Methyl Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 46.25 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 19.08 parts by weight of an methyl amide based on UNICID®        350 (obtained from Baker Petrolite) and described in Example 4);    -   about 17.13 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 2 of U.S. Pat. No. 6,860,930, which is incorporated        by reference herein in its entirety;    -   about 11.62 parts by weight KE100;    -   about 2.17 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based,        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for 45 minutes. The resulting inkwas then filtered through a combination of Whatman #3 and 0.2 micron NAEfilters and placed in a Mott filter assembly. Filtration was supportedby the addition of about 1 percent by weight FILTER-AID obtained fromFluka Chemika, Switzerland, and proceeded at a temperature of about 135°C. until complete after 6 hours. The ink base was poured into moldscontaining about 31 grams of the colorless ink base and allowed to cool.The viscosity was about 10.52 cps at about 110° C.

Preparation of Example E with Di-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 38.9 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 24.48 parts by weight of the iso-stearyl gel di-amide        described in Example 13;    -   about 17.26 parts by weight tetra-amide resin obtained from the        reaction of one equivalent of a C-36 dimer acid (obtained from        Uniqema, New Castle, Del.) with two equivalents of ethylene        diamine and UNICID® 700 (obtained from Baker Petrolite), a long        chain hydrocarbon having a terminal carboxylic acid group,        prepared as described in Example 1 of U.S. Pat. No. 6,174,937;    -   about 11.04 parts by weight of a parts by weight urethane resin        obtained from the reaction of two equivalents of ABITOL® E        hydroabietyl alcohol (obtained from Hercules Inc.) and one        equivalent of isophorone diisocyanate, prepared as described in        Example 1 of U.S. Pat. No. 5,782,966;    -   about 2.2 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.20 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 10.82 cps atabout 140° C.

Preparation of Example F with Di-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 42.16 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 24.48 parts by weight of the iso-stearyl gel di-amide        described in Example 13;    -   about 16.26 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 11.15 parts by weight KE100;    -   about 2.2 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity was about 10.93 cps at about 110° C.

Preparation of Example G with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 46.7 parts by weight, polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 17.42 parts by weight of the tetra-amide based on UNICID®        700 described in Example 22;    -   about 12.76 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 12.0 parts by weight of a parts by weight urethane resin        obtained from the reaction of two equivalents of ABITOL® E        hydroabietyl alcohol (obtained from Hercules Inc.) and one        equivalent of isophorone diisocyanate, prepared as described in        Example 1 of U.S. Pat. No. 5,782,966;    -   about 4.99 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 9.62 cps atabout 140° C.

Preparation of Example H with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 46.7 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 17.42 parts by weight of the gel tetra-amide based on        UNICID® 550 described in Example 23;    -   about 12.76 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 12.0 parts by weight of a parts by weight urethane resin        obtained from the reaction of two equivalents of ABITOL® E        hydroabietyl alcohol (obtained from Hercules Inc.) and one        equivalent of isophorone diisocyanate, prepared as described in        Example 1 of U.S. Pat. No. 5,782,966;    -   about 4.99 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 9.98 cps atabout 140° C.

Preparation of Example I with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 46.7 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 17.42 parts by weight of the gel tetra-amide based on        UNICID® 425 described in Example 23;    -   about 12.76 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 12 parts by weight of a parts by weight urethane resin        obtained from the reaction of two equivalents of ABITOL® E        hydroabietyl alcohol (obtained from Hercules Inc.) and one        equivalent of isophorone diisocyanate, prepared as described in        Example 1 of U.S. Pat. No. 5,782,966;    -   about 4.99 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 10.26 cps atabout 140° C.

Preparation of Example J with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 50.0 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 15.6 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 15.4 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 13.08 parts by weight of the gel tetra-amide based on        UNICID® 700 described in Example 22;    -   about 2.17 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.20 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after 6 hours. The ink base was pouredinto molds containing about 31 grams of the colorless ink base andallowed to cool. The viscosity was about 11.5 cps at about 110° C.

Preparation of Example K with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 50.8 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 15.6 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 15.4 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 12.28 parts by weight of the gel tetra-amide based on        UNICID® 550 described in Example 23;    -   about 2.17 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.20 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity was 10.86 cps at about 110° C.

Preparation of Example L with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 47.46 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 22.68 parts by weight of the gel tetra-amide based on        hydroxystearic acid described in Example 28;    -   about 13.6 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 6.14 parts by weight of a parts by weight urethane resin        obtained from the reaction of two equivalents of ABITOL® E        hydroabietyl alcohol (obtained from Hercules Inc.) and one        equivalent of isophorone diisocyanate, prepared as described in        Example 1 of U.S. Pat. No. 5,782,966;    -   about 4.0 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in Example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 11.02 cps atabout 140° C.

Preparation of Example M with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 50.0 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 28.85 parts by weight of the gel tetra-amide based on        hydroxystearic acid described in Example 28;    -   about 15.4 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 2.0 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.20 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity was about 11.64 cps at about 110° C.

Preparation of Example N with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 48.86 parts by weight polyethylene wax (PE 655®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 27.64 parts by weight of the gel tetra-amide based on        isostearic acid described in Example 30;    -   about 13.38 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 4.0 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.20 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 5.92 parts of a cyan dye as described in example 4 of U.S.        Pat. No. 5,919,839.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity of the ink was about 11.02 cps atabout 140° C.

Preparation of Example O with Tetra-Amide

An ink was prepared by melting, admixing, and filtering the followingingredients:

-   -   about 48.2 parts by weight polyethylene wax (PE 500®, obtained        from Baker Petrolite) of the formula CH₃(CH₂)₅₀CH₃);    -   about 17.2 parts by weight stearyl stearamide wax (KEMAMIDE®        S-180, obtained from Crompton Corporation);    -   about 15.4 parts by weight tri-amide resin obtained from the        reaction of one equivalent of a Jeffamine available from        Huntsman International LLC and 3 equivalents of a C-36 UNICID®        550 (obtained from Baker Petrolite), a long chain hydrocarbon        having a terminal carboxylic acid group, prepared as described        in Example 1 of U.S. Pat. No. 6,174,937;    -   about 13.45 parts by weight of the gel tetra-amide based on        isostearic acid described in Example 30;    -   about 2 parts by weight urethane resin that is the adduct of        three equivalents of stearyl isocyanate and a glycerol-based        alcohol, prepared as described in Example 4 of U.S. Pat. No.        6,309,453;    -   about 0.2 parts by weight NAUGUARD® 445 antioxidant (obtained        from Uniroyal Chemical Co.); and    -   about 3.55 parts of a cyan dye as described in Examples 5-10 of        U.S. Pat. No. 6,472,523.

Thereafter, about 600 grams of the ink carrier components as listedabove in the percentages as listed above were added to a 1 liter beakerand heated in an oven at about 135° C. until molten. Subsequently, thebeaker was inserted into a heating mantle set to about 135° C. and thecontents of the beaker were stirred for about 45 minutes. The resultingink was then filtered through a combination of Whatman #3 and 0.2 micronNAE filters and placed in a Mott filter assembly. Filtration wassupported by the addition of about 1 percent by weight FILTER-AIDobtained from Fluka Chemika, Switzerland, and proceeded at a temperatureof about 135° C. until complete after about 6 hours. The ink base waspoured into molds containing about 31 grams of the colorless ink baseand allowed to cool. The viscosity was about 12.14 cps at about 110° C.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also,various presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art, and are also intended to beencompassed by the following claims.

1. An ink composition comprising: stearyl stearamide, N,N′-ethylenebisoleamide, at least one wax, at least one antioxidant, and at leastone solvent dye colorant.
 2. The ink composition according to claim 1,wherein the at least one wax comprises a mixture of at least oneFischer-Tropsch wax and at least one fatty acid ester wax.
 3. The inkcomposition according to claim 1, wherein the at least one antioxidantis


4. The ink composition according to claim 2, wherein the at least oneantioxidant is


5. The ink composition according to claim 1, wherein the at least onesolvent dye colorant is solvent black.
 6. The ink composition accordingto claim 2, wherein the at least one solvent dye colorant is solventblack.
 7. The ink composition according to claim 3, wherein the at leastone solvent dye colorant is solvent black.
 8. The ink compositionaccording to claim 1, wherein the at least one solvent dye colorant issolvent yellow.
 9. The ink composition according to claim 2, wherein theat least one solvent dye colorant is solvent yellow.
 10. The inkcomposition according to claim 3, wherein the at least one solvent dyecolorant is solvent yellow.
 11. A phase change ink compositioncomprising an ink vehicle and a colorant, wherein the phase change inkis solid at temperatures of from about 20° C. to about 27° C. andexhibits a viscosity of from about 1 to about 20 centipoise (cP) at anelevated temperature at which the phase change ink is to be jetted,wherein the ink vehicle comprises stearyl stearamide, N,N′-ethylenebisoleamide, at least one wax, and at least one antioxidant, and whereinthe colorant comprises at least one solvent dye colorant.
 12. The phasechange ink composition according to claim 11, wherein the at least onewax comprises a mixture of at least one Fischer-Tropsch wax and at leastone fatty acid ester wax.
 13. The phase change ink composition accordingto claim 11, wherein the at least one antioxidant is


14. The phase change ink composition according to claim 12, wherein theat least one antioxidant is


15. The phase change ink composition according to claim 11, wherein theat least one solvent dye colorant is solvent black.
 16. The phase changeink composition according to claim 12, wherein the at least one solventdye colorant is solvent black.
 17. The phase change ink compositionaccording to claim 13, wherein the at least one solvent dye colorant issolvent black.
 18. The phase change ink composition according to claim11, wherein the at least one solvent dye colorant is solvent yellow. 19.The phase change ink composition according to claim 12, wherein the atleast one solvent dye colorant is solvent yellow.
 20. The phase changeink composition according to claim 13, wherein the at least one solventdye colorant is solvent yellow.